Olefin metathesis catalysts

ABSTRACT

This invention relates generally to metathesis catalysts and the use of such catalysts in the metathesis of olefins and olefin compounds, more particularly, in the use of such catalysts in Z and E selective olefin metathesis reactions. The invention has utility in the fields of organometallics and organic synthesis.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional PatentApplication No. 62/377,337, filed Aug. 19, 2016, and the benefit of U.S.Provisional Patent Application No. 62/265,575, filed Dec. 10, 2015, thecontents of which are incorporated herein by reference.

TECHNICAL FIELD

This invention relates generally to metathesis catalysts and the use ofsuch catalysts in the metathesis of olefins and olefin compounds, moreparticularly, in the use of such catalysts in Z or E selective olefinmetathesis reactions, particularly Z or E selective cross metathesisreactions. The invention has utility in the fields of organometallicsand organic synthesis.

BACKGROUND

The transition-metal catalyzed olefin metathesis reaction is animportant methodology for the construction of new carbon-carbon doublebonds (see (a) Fürstner, A. Angew. Chem., Int. Ed. 2000, 39, 3013. (b)Trnka, T. M.; Grubbs, R. H. Acc. Chem. Res. 2001, 34, 18. (c) Schrock,R. R. Chem. Rev. 2002, 102, 145. (d) Schrock, R. R.; Hoveyda, A. H.Angew. Chem., Int. Ed. 2003, 42, 4592. (e) Vougioukalakis, G.; Grubbs,R. H. Chem. Rev. 2009, 110, 1746. (f) Samojlowicz, C.; Bieniek, M.;Grela, K. Chem. Rev. 2009, 109, 3708).

Since its discovery metathesis has been employed with success in anumber of fields, including biochemistry, materials science, and greenchemistry (see (a) Binder, J. B.; Raines, R. T. Curr. Opin. Chem. Biol.2008, 12, 767; (b) Leitgeb, A.; Wappel, J.; Slugovc, C. Polymer 2010,51, 2927; (c) Sutthasupa, S.; Shiotsuki, M.; Sanda, F. Polym. J. 2010,42, 905; (d) Liu, X.; Basu, A. J. Organomet. Chem. 2006, 691, 5148).

However, an ongoing challenge in cross metathesis (CM) reactions hasbeen the control of stereoselectivity, particularly the retention of thestereoselectivity of the Z or E olefin, as metathesis catalystsgenerally favor formation of the thermodynamically preferred E-olefin(see Grubbs, R. H. Handbook of Metathesis; Wiley-VCH: Weinheim, 2003).

Work by Schrock and Hoveyda et. al. resulted in the development ofZ-selective metathesis catalysts using molybdenum and tungsten, allowingfor the synthesis of Z-olefins via metathesis (see (a) Flook, M. M.;Jiang, A. J.; Schrock, R. R.; Müller, P.; Hoveyda, A. H. J. Am. Chem.Soc. 2009, 131, 7962. (b) Marinescu, S. C.; Schrock, R. R.; Müller, P.;Takase, M. K.; Hoveyda, A. H. Organometallics 2011, 30, 1780. (c) Meek,S. J.; O'Brien, R. V.; Llaveria, J.; Schrock, R. R.; Hoveyda, A. H.Nature 2011, 471, 461. (d) Jiang, A. J.; Zhao, Y.; Schrock, R. R.;Hoveyda, A. H. J. Am. Chem. Soc. 2009, 131, 16630. (e) WO 2009/094201A2).

Work by Grubbs et al. resulted in the development of Z-selectiveruthenium metathesis catalysts containing a chelating N-heterocycliccarbene (NHC) ligand, allowing for the synthesis of Z-olefins viametathesis (see (a) Endo, K.; Grubbs, R. H. J. Am. Chem. Soc. 2011, 133,8525. (b) Keitz, B. K.; Endo, K.; Herbert, M. B.; Grubbs, R. H. J. Am.Chem. Soc. 2011, 133, 9686. (c) Keitz, B. K.; Endo, K.; Patel, P. R.;Herbert, M. B.; Grubbs, R. H. J. Am. Chem. Soc. 2011, 134, 693. (d) WO2012/097379 A2. (e) WO 2014/093687 A1).

Work by Hoveyda et al. resulted in the development of Z-selectiveruthenium metathesis catalysts containing a NHC ligand and a bidentateanionic ligand, allowing for the synthesis of Z-olefins via metathesis(see (a) Khan, R. K. M.; Torker, S.; Hoveyda, A. H. J. Am. Chem. Soc.2013, 135, 10258. (b) WO 2014/201300 A1. (c) Koh, M. J.; Khan, K. M.;Torker, S.; Yu, M.; Mikus, M. S.; Hoveyda, A. M. Nature 2015, 517, 181).

Despite the advances achieved, a continuing need exists for improvedcatalysts, particularly stereoselective and stereoretentive olefinmetathesis catalysts which provide improved activity and Z or Eselectivity in olefin metathesis reactions, particularly in crossmetathesis reactions. The invention is directed to addressing one ormore of the aforementioned concerns.

SUMMARY

In the course of evaluating Z-selective olefin metathesis catalysts forselective reactions with mixtures of cis and trans 5-tetradecene (5C14)(14:86 Z:E), C765 was found to afford a thermodynamic distribution ofproducts after 5 hours (Scheme 1). Prompted by this unusual apparentlack of selectivity, a more thorough investigation into this family ofcatalysts was initiated.

In one embodiment, the invention provides a compound of Formula (I):

wherein:

X is O or S; Y is O or S; Z is N or CR³²; W is O, NR³³ or S;

R¹ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R² is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl, optionally substitutedC₃₋₈ cycloalkenyl or together with R³ may form a polycyclic ring;R³ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl or together with R² may form a polycyclic ring;R⁴ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R⁵ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R⁶ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R⁷ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R⁸ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R⁹ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R¹⁰ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R¹¹ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R¹² is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R¹³ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R¹⁴ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R¹⁵ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl, or together with R¹⁶ may form an optionallysubstituted polycyclic ring;R¹⁶ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl, or together with R¹⁵ may form an optionallysubstituted polycyclic ring;R¹⁷ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl, or together with R¹⁸ may form an optionallysubstituted polycyclic ring;R¹⁸ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl, or together with R¹⁷ may form an optionallysubstituted polycyclic ring;R¹⁹ is hydrogen, optionally substituted C₁₋₂₄ alkyl, —C(O)R²⁵,optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R²⁰ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R²¹ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R²² is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R²³ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R²⁴ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R²⁵ is OH, OR³⁰, NR²⁷R²⁸, optionally substituted C₁₋₂₄ alkyl, optionallysubstituted C₃₋₈ cycloalkyl, optionally substituted heterocycle,optionally substituted C₅₋₂₄ aryl or optionally substituted C₃₋₈cycloalkenyl,R²⁶ is H, optionally substituted C₁₋₂₄ alkyl, optionally substitutedC₃₋₈ cycloalkyl, optionally substituted heterocycle, optionallysubstituted C₅₋₂₄ aryl or optionally substituted C₃₋₈ cycloalkenyl;R²⁷ is H, optionally substituted C₁₋₂₄ alkyl, optionally substitutedC₃₋₈ cycloalkyl, optionally substituted heterocycle, optionallysubstituted C₅₋₂₄ aryl or optionally substituted C₃₋₈ cycloalkenyl;R²⁸ is H, optionally substituted C₁₋₈ alkyl, optionally substituted C₃₋₈cycloalkyl, optionally substituted heterocycle, optionally substitutedC₅₋₂₄ aryl or optionally substituted C₃₋₈ cycloalkenyl;R²⁹ is hydrogen, optionally substituted C₁₋₂₄ alkyl, OR²⁶, —NR²⁷R²⁸,optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R³⁰ is optionally substituted C₁₋₂₄ alkyl, optionally substituted C₃₋₈cycloalkyl, optionally substituted heterocycle, optionally substitutedC₅₋₂₄ aryl or optionally substituted C₃₋₈ cycloalkenyl;R³¹ is hydrogen, optionally substituted C₁₋₂₄ alkyl, optionallysubstituted C₃₋₈ cycloalkyl, optionally substituted heterocycle,optionally substituted C₅₋₂₄ aryl or optionally substituted C₃₋₈cycloalkenyl;R³² is hydrogen, optionally substituted C₁₋₂₄ alkyl, optionallysubstituted C₃₋₈ cycloalkyl, optionally substituted heterocycle,optionally substituted C₅₋₂₄ aryl or optionally substituted C₃₋₈cycloalkenyl;R³³ is hydrogen, optionally substituted C₁₋₂₄ alkyl, optionallysubstituted C₃₋₈ cycloalkyl, optionally substituted heterocycle,optionally substituted C₅₋₂₄ aryl or optionally substituted C₃₋₈cycloalkenyl; andm is 1 or 2.

In one embodiment, the invention provides a method for performing across metathesis reaction, comprising: contacting a first internalolefin reactant with a second internal olefin reactant in the presenceof a compound of Formula (I), under conditions effective to promote theformation of at least one cross metathesis product, where the firstinternal olefin reactant and the second internal olefin reactant may bethe same or different, where the first internal olefin reactant and thesecond internal olefin reactant are each in a Z-configuration; and wherethe at least one cross metathesis product is greater than about 80% Z.

In one embodiment, the invention provides a method for performing across metathesis reaction, comprising: contacting a first internalolefin reactant with a second internal olefin reactant in the presenceof a compound of Formula (I), under conditions effective to promote theformation of at least one cross metathesis product, where the firstinternal olefin reactant and the second internal olefin reactant may bethe same or different, where the first internal olefin reactant and thesecond internal olefin reactant are each in a Z-configuration; and wherethe at least one cross metathesis product is greater than about 90% Z.

In one embodiment, the invention provides a method for performing across metathesis reaction, comprising: contacting a first internalolefin reactant with a second internal olefin reactant in the presenceof a compound of Formula (I), under conditions effective to promote theformation of at least one cross metathesis product, where the firstinternal olefin reactant and the second internal olefin reactant may bethe same or different, where the first internal olefin reactant and thesecond internal olefin reactant are each in a Z-configuration; and wherethe at least one cross metathesis product is greater than about 95% Z.

In one embodiment, the invention provides a method for performing across metathesis reaction, comprising: contacting a first internalolefin reactant with a second internal olefin reactant in the presenceof a compound of Formula (I), under conditions effective to promote theformation of at least one cross metathesis product, where the firstinternal olefin reactant and the second internal olefin reactant may bethe same or different, where the first internal olefin reactant and thesecond internal olefin reactant are each in a Z-configuration; and wherethe at least one cross metathesis product is greater than about 99% Z.

In one embodiment, the invention provides a method for performing across metathesis reaction, comprising: contacting a first internalolefin reactant with a second internal olefin reactant in the presenceof a compound of Formula (I), under conditions effective to promote theformation of at least one cross metathesis product, where the firstinternal olefin reactant and the second internal olefin reactant may bethe same or different, where the first internal olefin reactant and thesecond internal olefin reactant are each in an E-configuration; andwhere the at least one cross metathesis product is greater than about80% E.

In one embodiment, the invention provides a method for performing across metathesis reaction, comprising: contacting a first internalolefin reactant with a second internal olefin reactant in the presenceof a compound of Formula (I), under conditions effective to promote theformation of at least one cross metathesis product, where the firstinternal olefin reactant and the second internal olefin reactant may bethe same or different, where the first internal olefin reactant and thesecond internal olefin reactant are each in an E-configuration; andwhere the at least one cross metathesis product is greater than about90% E.

In one embodiment, the invention provides a method for performing across metathesis reaction, comprising: contacting a first internalolefin reactant with a second internal olefin reactant in the presenceof a compound of Formula (I), under conditions effective to promote theformation of at least one cross metathesis product, where the firstinternal olefin reactant and the second internal olefin reactant may bethe same or different, where the first internal olefin reactant and thesecond internal olefin reactant are each in an E-configuration; andwhere the at least one cross metathesis product is greater than about95% E.

In one embodiment, the invention provides a method for performing across metathesis reaction, comprising: contacting a first internalolefin reactant with a second internal olefin reactant in the presenceof a compound of Formula (I), under conditions effective to promote theformation of at least one cross metathesis product, where the firstinternal olefin reactant and the second internal olefin reactant may bethe same or different, where the first internal olefin reactant and thesecond internal olefin reactant are each in an E-configuration; andwhere the at least one cross metathesis product is greater than about99% E.

In one embodiment, the invention provides a method for performing across metathesis reaction, comprising: contacting a first internalolefin reactant with a second terminal olefin reactant in the presenceof a compound of Formula (I), under conditions effective to promote theformation of at least one cross metathesis product, where the firstinternal olefin reactant is in a Z-configuration; and where the at leastone cross metathesis product is greater than about 80% Z.

In one embodiment, the invention provides a method for performing across metathesis reaction, comprising: contacting a first internalolefin reactant with a second terminal olefin reactant in the presenceof a compound of Formula (I), under conditions effective to promote theformation of at least one cross metathesis product, where the firstinternal olefin reactant is in a Z-configuration; and where the at leastone cross metathesis product is greater than about 90% Z.

In one embodiment, the invention provides a method for performing across metathesis reaction, comprising: contacting a first internalolefin reactant with a second terminal olefin reactant in the presenceof a compound of Formula (I), under conditions effective to promote theformation of at least one cross metathesis product, where the firstinternal olefin reactant is in a Z-configuration; and where the at leastone cross metathesis product is greater than about 95% Z.

In one embodiment, the invention provides a method for performing across metathesis reaction, comprising: contacting a first internalolefin reactant with a second terminal olefin reactant in the presenceof a compound of Formula (I), under conditions effective to promote theformation of at least one cross metathesis product, where the firstinternal olefin reactant is in a Z-configuration; and where the at leastone cross metathesis product is greater than about 99% Z.

In one embodiment, the invention provides a method for performing across metathesis reaction, comprising: contacting a first internalolefin reactant with a second terminal olefin reactant in the presenceof a compound of Formula (I), under conditions effective to promote theformation of at least one cross metathesis product, where the firstinternal olefin reactant is in an E-configuration; and where the atleast one cross metathesis product is greater than about 80% E.

In one embodiment, the invention provides a method for performing across metathesis reaction, comprising: contacting a first internalolefin reactant with a second terminal olefin reactant in the presenceof a compound of Formula (I), under conditions effective to promote theformation of at least one cross metathesis product, where the firstinternal olefin reactant is in an E-configuration; and where the atleast one cross metathesis product is greater than about 90% E.

In one embodiment, the invention provides a method for performing across metathesis reaction, comprising: contacting a first internalolefin reactant with a second terminal olefin reactant in the presenceof a compound of Formula (I), under conditions effective to promote theformation of at least one cross metathesis product, where the firstinternal olefin reactant is in an E-configuration; and where the atleast one cross metathesis product is greater than about 95% E.

In one embodiment, the invention provides a method for performing across metathesis reaction, comprising: contacting a first internalolefin reactant with a second terminal olefin reactant in the presenceof a compound of Formula (I), under conditions effective to promote theformation of at least one cross metathesis product, where the firstinternal olefin reactant is in an E-configuration; and where the atleast one cross metathesis product is greater than about 99% E.

In one embodiment, the invention provides for use of a compound ofFormula (I) in olefin metathesis. In one embodiment, the inventionprovides for use of a compound of Formula (I) in an olefin metathesisreaction. In one embodiment, the invention provides for use of acompound of Formula (I) in a Z-selective olefin metathesis reaction. Inone embodiment, the invention provides for use of a compound of Formula(I) in a Z-selective cross metathesis reaction.

In one embodiment, the invention provides for use of a compound ofFormula (I) in olefin metathesis. In one embodiment, the inventionprovides for use of a compound of Formula (I) in an olefin metathesisreaction. In one embodiment, the invention provides for use of acompound of Formula (I) in an E-selective olefin metathesis reaction. Inone embodiment, the invention provides for use of a compound of Formula(I) in an E-selective cross metathesis reaction.

In one embodiment, the invention provides a method for performing aZ-selective olefin metathesis reaction. In one embodiment, the inventionprovides a method for performing a Z-selective cross metathesisreaction.

In one embodiment, the invention provides a method for performing anE-selective olefin metathesis reaction. In one embodiment, the inventionprovides a method for performing an E-selective cross metathesisreaction.

These and other aspects of the invention will be apparent to the skilledartisan in light of the following detailed description and examples.

DETAILED DESCRIPTION Terminology and Definitions

Unless otherwise indicated, the invention is not limited to specificreactants, reaction conditions, or the like, as such may vary. It isalso to be understood that the terminology used herein is for thepurpose of describing particular embodiments and is not to beinterpreted as being limiting.

As used in the specification and the appended claims, the singular forms“a,” “an,” and “the” include plural referents unless the context clearlydictates otherwise. Thus, for example, reference to “an α-olefin”includes a single α-olefin as well as a combination or mixture of two ormore α-olefins, reference to “a substituent” encompasses a singlesubstituent as well as two or more substituents, and the like.

As used in the specification and the appended claims, the terms “forexample,” “for instance,” “such as,” or “including” are meant tointroduce examples that further clarify more general subject matter.Unless otherwise specified, these examples are provided only as an aidfor understanding the invention, and are not meant to be limiting in anyfashion.

In this specification and in the claims that follow, reference will bemade to a number of terms, which shall be defined to have the followingmeanings.

The term “alkyl” as used herein refers to a linear, branched, or cyclicsaturated hydrocarbon group typically although not necessarilycontaining 1 to about 24 carbon atoms, preferably 1 to about 12 carbonatoms, such as methyl (Me), ethyl (Et), n-propyl (Pr or n-Pr), isopropyl(i-Pr), n-butyl (Bu or n-Bu), isobutyl (i-Bu), t-butyl (t-Bu), octyl(Oct), decyl, and the like, as well as cycloalkyl groups such ascyclopentyl (Cp), cyclohexyl (Cy) and the like. Generally, althoughagain not necessarily, alkyl groups herein contain 1 to about 8 carbonatoms. The term “lower alkyl” refers to an alkyl group of 1 to 6 carbonatoms, and the specific term “cycloalkyl” refers to a cyclic alkylgroup, typically having 3 to 8, preferably 5 to 7, carbon atoms. Theterm “substituted alkyl” refers to alkyl substituted with one or moresubstituent groups, and the terms “heteroatom-containing alkyl” and“heteroalkyl” refer to alkyl in which at least one carbon atom isreplaced with a heteroatom. If not otherwise indicated, the terms“alkyl” and “lower alkyl” include linear, branched, cyclic,unsubstituted, substituted, and/or heteroatom-containing alkyl and loweralkyl, respectively.

The term “alkylene” as used herein refers to a difunctional linear,branched, or cyclic alkyl group, where “alkyl” is as defined above.

The term “alkenyl” as used herein refers to a linear, branched, orcyclic hydrocarbon group of 2 to about 24 carbon atoms containing atleast one double bond, such as ethenyl, n-propenyl, isopropenyl,n-butenyl, isobutenyl, octenyl, decenyl, tetradecenyl, hexadecenyl,eicosenyl, tetracosenyl, and the like. Preferred alkenyl groups hereincontain 2 to about 12 carbon atoms. The term “lower alkenyl” refers toan alkenyl group of 2 to 6 carbon atoms, and the specific term“cycloalkenyl” refers to a cyclic alkenyl group, preferably having 3 to8 carbon atoms. The term “substituted alkenyl” refers to alkenylsubstituted with one or more substituent groups, and the terms“heteroatom-containing alkenyl” and “heteroalkenyl” refer to alkenyl inwhich at least one carbon atom is replaced with a heteroatom. If nototherwise indicated, the terms “alkenyl” and “lower alkenyl” includelinear, branched, cyclic, unsubstituted, substituted, and/orheteroatom-containing alkenyl and lower alkenyl, respectively.

The term “alkenylene” as used herein refers to a difunctional linear,branched, or cyclic alkenyl group, where “alkenyl” is as defined above.

The term “alkynyl” as used herein refers to a linear or branchedhydrocarbon group of 2 to about 24 carbon atoms containing at least onetriple bond, such as ethynyl, n-propynyl, and the like. Preferredalkynyl groups herein contain 2 to about 12 carbon atoms. The term“lower alkynyl” refers to an alkynyl group of 2 to 6 carbon atoms. Theterm “substituted alkynyl” refers to alkynyl substituted with one ormore substituent groups, and the terms “heteroatom-containing alkynyl”and “heteroalkynyl” refer to alkynyl in which at least one carbon atomis replaced with a heteroatom. If not otherwise indicated, the terms“alkynyl” and “lower alkynyl” include linear, branched, unsubstituted,substituted, and/or heteroatom-containing alkynyl and lower alkynyl,respectively.

The term “alkynylene” as used herein refers to a difunctional alkynylgroup, where “alkynyl” is as defined above.

The term “alkoxy” as used herein refers to an alkyl group bound througha single, terminal ether linkage; that is, an “alkoxy” group may berepresented as —O-alkyl where alkyl is as defined above. A “loweralkoxy” group refers to an alkoxy group containing 1 to 6 carbon atoms.Analogously, “alkenyloxy” and “lower alkenyloxy” respectively refer toan alkenyl and lower alkenyl group bound through a single, terminalether linkage, and “alkynyloxy” and “lower alkynyloxy” respectivelyrefer to an alkynyl and lower alkynyl group bound through a single,terminal ether linkage.

The term “aryl” as used herein, and unless otherwise specified, refersto an aromatic substituent containing a single aromatic ring or multiplearomatic rings that are fused together, directly linked, or indirectlylinked (such that the different aromatic rings are bound to a commongroup such as a methylene or ethylene moiety). Preferred aryl groupscontain 5 to 24 carbon atoms, and particularly preferred aryl groupscontain 6 to 10 carbon atoms. Exemplary aryl groups contain one aromaticring or two fused or linked aromatic rings, e.g., phenyl (Ph), naphthyl,biphenyl, diphenylether, diphenylamine, benzophenone, phenanthryl andthe like. “Substituted aryl” refers to an aryl moiety substituted withone or more substituent groups, and the terms “heteroatom containingaryl” and “heteroaryl” refer to aryl substituents in which at least onecarbon atom is replaced with a heteroatom, as will be described infurther detail herein.

The term “aryloxy” as used herein refers to an aryl group bound througha single, terminal ether linkage, wherein “aryl” is as defined above. An“aryloxy” group may be represented as —O-aryl where aryl is as definedabove. Preferred aryloxy groups contain 5 to 24 carbon atoms, andparticularly preferred aryloxy groups contain 6 to 10 carbon atoms.Examples of aryloxy groups include, without limitation, phenoxy,o-halo-phenoxy, m-halo-phenoxy, p-halo-phenoxy, o-methoxy-phenoxy,m-methoxy-phenoxy, p-methoxy-phenoxy, 2,4-dimethoxy-phenoxy,3,4,5-trimethoxy-phenoxy, and the like.

The term “alkaryl” refers to an aryl group with an alkyl substituent,and the term “aralkyl” refers to an alkyl group with an arylsubstituent, wherein “aryl” and “alkyl” are as defined above. Preferredalkaryl and aralkyl groups contain 6 to 24 carbon atoms, andparticularly preferred alkaryl and aralkyl groups contain 6 to 16 carbonatoms. Alkaryl groups include, without limitation, p-methylphenyl,2,4-dimethylphenyl, p-cyclohexylphenyl, 2,7-dimethylnaphthyl,7-cyclooctylnaphthyl, 3-ethyl-cyclopenta-1,4-diene, and the like.Examples of aralkyl groups include, without limitation, benzyl,2-phenyl-ethyl, 3-phenyl-propyl, 4-phenyl-butyl, 5-phenyl-pentyl,4-phenylcyclohexyl, 4-benzylcyclohexyl, 4-phenylcyclohexylmethyl,4-benzylcyclohexylmethyl, and the like. The terms “alkaryloxy” and“aralkyloxy” refer to substituents of the formula —OR wherein R isalkaryl or aralkyl, respectively, as just defined.

The term “acyl” refers to substituents having the formula —(CO)-alkyl,—(CO)-aryl, —(CO)-aralkyl, —(CO)-alkaryl, —(CO)-alkenyl, or—(CO)-alkynyl, and the term “acyloxy” refers to substituents having theformula —O(CO)-alkyl, —O(CO)-aryl, —O(CO)-aralkyl, —O(CO)-alkaryl,—O(CO)-alkenyl, or —(CO)-alkynyl wherein “alkyl,” “aryl”, “aralkyl”,“alkaryl”, “alkenyl”, and “alkynyl” are as defined above. The acetoxygroup (—O(CO)CH₃; often abbreviated as -OAc) is a common example of anacyloxy group.

The terms “cyclic” and “ring” refer to alicyclic or aromatic groups thatmay or may not be substituted and/or heteroatom containing, and that maybe monocyclic, bicyclic, or polycyclic. The term “alicyclic” is used inthe conventional sense to refer to an aliphatic cyclic moiety, asopposed to an aromatic cyclic moiety, and may be monocyclic, bicyclic orpolycyclic.

The terms “polycyclic ring” refer to alicyclic or aromatic groups thatmay or may not be substituted and/or heteroatom containing, and thathave at least two closed rings tethered, fused, linked via a single bondor bridged. Polycyclic rings include without limitation naphthyl,biphenyl, phenanthryl and the like.

The terms “halo” and “halogen” and “halide” are used in the conventionalsense to refer to a fluoro, chloro, bromo, or iodo substituent.

“Hydrocarbyl” refers to univalent hydrocarbyl radicals containing 1 toabout 30 carbon atoms, preferably 1 to about 24 carbon atoms, mostpreferably 1 to about 12 carbon atoms, including linear, branched,cyclic, saturated and unsaturated species, such as alkyl groups, alkenylgroups, alkynyl groups, aryl groups, and the like. The term “lowerhydrocarbyl” refers to a hydrocarbyl group of 1 to 6 carbon atoms,preferably 1 to 4 carbon atoms, and the term “hydrocarbylene” refers toa divalent hydrocarbyl moiety containing 1 to about 30 carbon atoms,preferably 1 to about 24 carbon atoms, most preferably 1 to about 12carbon atoms, including linear, branched, cyclic, saturated andunsaturated species. The term “lower hydrocarbylene” refers to ahydrocarbylene group of 1 to 6 carbon atoms. “Substituted hydrocarbyl”refers to hydrocarbyl substituted with one or more substituent groups,and the terms “heteroatom-containing hydrocarbyl” and“heterohydrocarbyl” refer to hydrocarbyl in which at least one carbonatom is replaced with a heteroatom. Similarly, “substitutedhydrocarbylene” refers to hydrocarbylene substituted with one or moresubstituent groups, and the terms “heteroatom-containing hydrocarbylene”and heterohydrocarbylene” refer to hydrocarbylene in which at least onecarbon atom is replaced with a heteroatom. Unless otherwise indicated,the term “hydrocarbyl” and “hydrocarbylene” are to be interpreted asincluding substituted and/or heteroatom-containing hydrocarbyl andhydrocarbylene moieties, respectively.

The term “heteroatom-containing” as in a “heteroatom-containinghydrocarbyl group” refers to a hydrocarbon molecule or a hydrocarbylmolecular fragment in which one or more carbon atoms is replaced with anatom other than carbon, e.g., nitrogen, oxygen, sulfur, phosphorus orsilicon, typically nitrogen, oxygen or sulfur. Similarly, the term“heteroalkyl” refers to an alkyl substituent that isheteroatom-containing, the term “heterocyclic” refers to a cyclicsubstituent that is heteroatom-containing, the terms “heteroaryl” and“heteroaromatic” respectively refer to “aryl” and “aromatic”substituents that are heteroatom-containing, and the like. It should benoted that a “heterocyclic” group or compound may or may not bearomatic, and further that “heterocycles” may be monocyclic, bicyclic,or polycyclic as described above with respect to the term “aryl.”Examples of heteroalkyl groups include without limitation alkoxyaryl,alkylsulfanyl-substituted alkyl, N-alkylated amino alkyl, and the like.Examples of heteroaryl substituents include without limitation pyrrolyl,pyrrolidinyl, pyridinyl, quinolinyl, indolyl, pyrimidinyl, imidazolyl,1,2,4-triazolyl, tetrazolyl, etc., and examples of heteroatom-containingalicyclic groups include without limitation pyrrolidino, morpholino,piperazino, piperidino, etc.

By “substituted” as in “substituted hydrocarbyl,” “substituted alkyl,”“substituted aryl,” and the like, as alluded to in some of theaforementioned definitions, is meant that in the hydrocarbyl, alkyl,aryl, or other moiety, at least one hydrogen atom bound to a carbon (orother) atom is replaced with one or more non-hydrogen substituents.Examples of such substituents include, without limitation: functionalgroups referred to herein as “Fn,” such as halo, hydroxyl, sulfhydryl,C₁-C₂₄ alkoxy, C₂-C₂₄ alkenyloxy, C₂-C₂₄ alkynyloxy, C₅-C₂₄ aryloxy,C₆-C₂₄ aralkyloxy, C₆-C₂₄ alkaryloxy, acyl (including C₂-C₂₄alkylcarbonyl (—CO-alkyl) and C₆-C₂₄ arylcarbonyl (—CO-aryl)), acyloxy(—O-acyl, including C₂-C₂₄ alkylcarbonyloxy (—O—CO-alkyl) and C₆-C₂₄arylcarbonyloxy (—O—CO-aryl)), C₂-C₂₄ alkoxycarbonyl (—(CO)—O-alkyl),C₆-C₂₄ aryloxycarbonyl (—(CO)—O-aryl), halocarbonyl (—CO)—X where X ishalo), C₂-C₂₄ alkylcarbonato (—O—(CO)—O-alkyl), C₆-C₂₄ arylcarbonato(—O—(CO)—O-aryl), carboxy (—COOH), carboxylato (—COO″), carbamoyl(—(CO)—NH₂), mono-(C₁-C₂₄ alkyl)-substituted carbamoyl (—(CO)—NH(C₁-C₂₄alkyl)), di-(C₁-C₂₄ alkyl)-substituted carbamoyl (—(CO)—N(C₁-C₂₄alkyl)₂), mono-(C₁-C₂₄ haloalkyl)-substituted carbamoyl (—(CO)—NH(C₁-C₂₄haloalkyl)), di-(C₁-C₂₄ haloalkyl)-substituted carbamoyl (—(CO)—N(C₁-C₂₄haloalkyl)₂), mono-(C₅-C₂₄ aryl)-substituted carbamoyl (—(CO)—NH-aryl),di-(C₅-C₂₄ aryl)-substituted carbamoyl (—(CO)—N(C₅-C₂₄ aryl)₂),di-N—(C₁-C₂₄ alkyl), N—(C₅-C₂₄ aryl)-substituted carbamoyl(—(CO)—N(C₁-C₂₄ alkyl)(C₅-C₂₄ aryl), thiocarbamoyl (—(CS)—NH₂),mono-(C₁-C₂₄ alkyl)-substituted thiocarbamoyl (—(CS)—NH(C₁-C₂₄ alkyl)),di-(C₁-C₂₄ alkyl)-substituted thiocarbamoyl (—(CS)—N(C₁-C₂₄ alkyl)₂),mono-(C₅-C₂₄ aryl)-substituted thiocarbamoyl (—(CS)—NH-aryl), di-(C₅-C₂₄aryl)-substituted thiocarbamoyl (—(CS)—N(C₅-C₂₄ aryl)₂), di-N—(C₁-C₂₄alkyl), N—(C₅-C₂₄ aryl)-substituted thiocarbamoyl (—(CS)—N(C₁-C₂₄alkyl)(C₅-C₂₄ aryl), carbamido (—NH—(CO)—NH₂), cyano(—C≡N), cyanato(—O—C≡N), thiocyanato (—S—C≡N), isocyanate (-NisCisO), thioisocyanate(-NisCisS), formyl (—(CO)—H), thioformyl (—(CS)—H), amino (—NH₂),mono-(C₁-C₂₄ alkyl)-substituted amino (—NH(C₁-C₂₄ alkyl), di-(C₁-C₂₄alkyl)-substituted amino ((—N(C₁-C₂₄ alkyl)₂), mono-(C₅-C₂₄aryl)-substituted amino (—NH(C₅-C₂₄ aryl), di-(C₅-C₂₄ aryl)-substitutedamino (—N(C₅-C₂₄ aryl)₂), C₂-C₂₄ alkylamido (—NH—(CO)-alkyl), C₆-C₂₄arylamido (—NH—(CO)-aryl), imino (-CRisNH where, R includes withoutlimitation hydrogen, C₁-C₂₄ alkyl, C₅-C₂₄ aryl, C₆-C₂₄ alkaryl, C₆-C₂₄aralkyl, etc.), C₂-C₂₀ alkylimino (-CRisN(alkyl), where R includeswithout limitation hydrogen, C₁-C₂₄ alkyl, C₅-C₂₄ aryl, C₆-C₂₄ alkaryl,C₆-C₂₄ aralkyl, etc.), arylimino (-CRisN(aryl), where R includes withoutlimitation hydrogen, C₁-C₂₀ alkyl, C₅-C₂₄ aryl, C₆-C₂₄ alkaryl, C₆-C₂₄aralkyl, etc.), nitro (—NO₂), nitroso (—NO), sulfo (—SO₂—OH), sulfonato(—SO₂—O—), C₁-C₂₄ alkylsulfanyl (—S-alkyl; also termed “alkylthio”),C₅-C₂₄ arylsulfanyl (—S-aryl; also termed “arylthio”), C₁-C₂₄alkylsulfinyl (—(SO)-alkyl), C₅-C₂₄ arylsulfinyl (—(SO)-aryl), C₁-C₂₄alkylsulfonyl (—SO₂-alkyl), C₁-C₂₄ monoalkylaminosulfonyl (—SO₂—N(H)alkyl), C₁-C₂₄ dialkylaminosulfonyl (—SO₂—N(alkyl)₂), C₅-C₂₄arylsulfonyl (—SO₂-aryl), boryl (—BH₂), borono (—B(OH)₂), boronato(—B(OR)₂ where R includes without limitation alkyl or otherhydrocarbyl), phosphono (—P(O)(OH)₂), phosphonato (—P(O)(O″)₂),phosphinato (—P(O)(O)), phospho (—PO₂), phosphino (—PH₂), silyl (—SiR₃wherein R is hydrogen or hydrocarbyl), and silyloxy (—O-silyl); and thehydrocarbyl moieties C₁-C₂₄ alkyl (preferably C₁-C₁₂ alkyl, morepreferably C₁-C₆ alkyl), C₂-C₂₄ alkenyl (preferably C₂-C₁₂ alkenyl, morepreferably C₂-C₆ alkenyl), C₂-C₂₄ alkynyl (preferably C₂-C₁₂ alkynyl,more preferably C₂-C₆ alkynyl), C₅-C₂₄ aryl (preferably C₅-C₁₄ aryl),C₆-C₂₄ alkaryl (preferably C₆-C₁₆ alkaryl), and C₆-C₂₄ aralkyl(preferably C₆-C₁₆ aralkyl).

By “functionalized” as in “functionalized hydrocarbyl,” “functionalizedalkyl,” “functionalized olefin,” “functionalized cyclic olefin,” and thelike, is meant that in the hydrocarbyl, alkyl, olefin, cyclic olefin, orother moiety, at least one hydrogen atom bound to a carbon (or other)atom is replaced with one or more functional groups such as thosedescribed hereinabove. The term “functional group” is meant to includeany functional species that is suitable for the uses described herein.In particular, as used herein, a functional group would necessarilypossess the ability to react with or bond to corresponding functionalgroups on a substrate surface.

In addition, the aforementioned functional groups may, if a particulargroup permits, be further substituted with one or more additionalfunctional groups or with one or more hydrocarbyl moieties such as thosespecifically enumerated above. Analogously, the above mentionedhydrocarbyl moieties may be further substituted with one or morefunctional groups or additional hydrocarbyl moieties such as thosespecifically mentioned above. Analogously, the above-mentionedhydrocarbyl moieties may be further substituted with one or morefunctional groups or additional hydrocarbyl moieties as noted above.

“Optional” or “optionally” means that the subsequently describedcircumstance may or may not occur, so that the description includesinstances where the circumstance occurs and instances where it does not.For example, the phrase “optionally substituted” means that anon-hydrogen substituent may or may not be present on a given atom, and,thus, the description includes structures wherein a non-hydrogensubstituent is present and structures wherein a non-hydrogen substituentis not present.

The term “internal olefin” as used herein means an olefin wherein eachof the olefinic carbons (i.e., the carbons of the carbon-carbon doublebond) is substituted by at least one non-hydrogen substituent. Theinternal olefin may be di-substituted, tri-substituted, ortetra-substituted (e.g., R^(1′)HC is CHR^(2′); R^(3′)R^(4′)C isCHR^(5′); R^(6′)R^(7′)C is CR^(8′)R^(9′); where R^(1′), R^(2′), R^(3′),R^(4′), R^(5′), R^(6′), R^(7′), R^(8′), and R^(9′) may be the same ordifferent and are each independently optionally substituted hydrocarbyl,optionally substituted heteroatom-containing hydrocarbyl, or afunctional group).

The term “terminal olefin” as used herein means an olefin wherein one ofthe olefinic carbons (i.e., the carbons of the carbon-carbon doublebond) is substituted by at least one non-hydrogen substituent and theother olefinic carbon is unsubstituted. The terminal olefin may bedi-substituted or mono-substituted (e.g., CH₂ is CHR^(10′) or CH₂ isCR^(11′)R^(12′); where R^(10′), R^(11′), and R^(12′) may be the same ordifferent and are each independently optionally substituted hydrocarbyl,optionally substituted heteroatom-containing hydrocarbyl, or afunctional group).

The term “reactant internal olefin” as used herein means an internalolefin present in an olefin compound used in a cross metathesis reactionwith another olefin compound to form a cross metathesis product. The“reactant internal olefin” may be di-substituted, tri-substituted, ortetra-substituted. The “reactant internal olefin” may have anE-configuration or a Z-configuration.

The term “product internal olefin” as used herein means an internalolefin present in a cross metathesis product formed by a crossmetathesis reaction, wherein each of the olefinic carbons (i.e., thecarbons of the carbon-carbon double bond) of the internal olefin issubstituted by at least one non-hydrogen substituent. The “productinternal olefin” may be di-substituted, tri-substituted, ortetra-substituted. The “product internal olefin” may have an Econfiguration or a Z-configuration.

The term “nil”, as used herein, means absent or nonexistent.

The term “hydroxyl” as used herein, represents a group of formula “—OH”.

The term “carbonyl” as used herein, represents a group of formula“—C(O)—”.

The term “ketone” as used herein, represents an organic compound havinga carbonyl group linked to a carbon atom such as —C(O)R^(x) whereinR^(x) can be alkyl, aryl, cycloalkyl, cycloalkenyl, heterocycle asdefined above.

The term “ester” as used herein, represents an organic compound having acarbonyl group linked to a carbon atom such as —C(O)OR^(x) wherein R^(x)can be alkyl, aryl, cycloalkyl, cycloalkenyl, heterocycle as definedabove.

The term “amine” as used herein, represents a group of formula“—NR^(x)R^(y),” wherein R^(x) and R^(y) can be the same or independentlyH, alkyl, aryl, cycloalkyl, cycloalkenyl, heterocycle as defined above.

The term “carboxyl” as used herein, represents a group of formula“—C(O)O—”.

The term “sulfonyl” as used herein, represents a group of formula“—SO₂”.

The term “sulfate” as used herein, represents a group of formula“—O—S(O)₂—O—”.

The term “sulfonate” as used herein, represents a group of the formula“—S(O)₂—O—”.

The term “carboxylic acid” as used herein, represents a group of formula“—C(O)OH”.

The term “nitro” as used herein, represents a group of formula “—NO₂”.

The term “cyano” as used herein, represents a group of formula “—CN”.

The term “amide” as used herein, represents a group of formula“—C(O)NR^(x)R^(y),” wherein R^(x) and R^(y) can be the same orindependently H, alkyl, aryl, cycloalkyl, cycloalkenyl, heterocycle asdefined above.

The term “sulfonamide” as used herein, represents a group of formula“—S(O)₂NR^(x)R^(y)” wherein R^(x) and R^(y) can be the same orindependently H, alkyl, aryl, cycloalkyl, cycloalkenyl, heterocycle asdefined above.

The term “sulfoxide” as used herein, represents a group of formula“—S(O)—”.

The term “phosphonic acid” as used herein, represents a group of formula“—P(O)(OH)₂”.

The term “phosphoric acid” as used herein, represents a group of formula“—OP(O)(OH)₂”.

The term “sulphonic acid” as used herein, represents a group of formula“—S(O)₂OH”.

The formula “H”, as used herein, represents a hydrogen atom.

The formula “O”, as used herein, represents an oxygen atom.

The formula “N”, as used herein, represents a nitrogen atom.

The formula “S”, as used herein, represents a sulfur atom.

Functional groups may be protected in cases where the functional groupinterferes with the metathesis catalyst, and any of the protectinggroups commonly used in the art may be employed. Acceptable protectinggroups may be found, for example, in Greene et al., Protective Groups inOrganic Synthesis, 3rd Ed. (New York: Wiley, 1999). Examples ofprotecting groups include acetals, cyclic acetals, boronate esters(boronates), cyclic boronate esters (cyclic boronates), carbonates, orthe like. Examples of protecting groups include cyclic acetals or cyclicboronate esters.

Olefin Metathesis Catalysts

In one embodiment, the invention provides a compound of Formula (I):

X is O or S; Y is O or S; Z is N or CR³²; W is O, NR³³ or S;

R¹ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R² is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl, optionally substitutedC₃₋₈ cycloalkenyl or together with R³ may form a polycyclic ring;R³ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl or together with R² may form a polycyclic ring;R⁴ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R⁵ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R⁶ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R⁷ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R⁸ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R⁹ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R¹⁰ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R¹¹ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R¹² is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R¹³ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R¹⁴ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R¹⁵ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl, or together with R¹⁶ may form an optionallysubstituted polycyclic ring;R¹⁶ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl, or together with R¹⁵ may form an optionallysubstituted polycyclic ring;R¹⁷ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl, or together with R¹⁸ may form an optionallysubstituted polycyclic ring;R¹⁸ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl, or together with R¹⁸ may form an optionallysubstituted polycyclic ring;R¹⁹ is hydrogen, optionally substituted C₁₋₂₄ alkyl, —C(O)R²⁵,optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R²⁰ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R²¹ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R²² is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R²³ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R²⁴ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R²⁵ is OH, OR³⁰, NR²⁷R²⁸, optionally substituted C₁₋₂₄ alkyl, optionallysubstituted C₃₋₈ cycloalkyl, optionally substituted heterocycle,optionally substituted C₅₋₂₄ aryl or optionally substituted C₃₋₈cycloalkenyl,R²⁶ is H, optionally substituted C₁₋₂₄ alkyl, optionally substitutedC₃₋₈ cycloalkyl, optionally substituted heterocycle, optionallysubstituted C₅₋₂₄ aryl or optionally substituted C₃₋₈ cycloalkenyl;R²⁷ is H, optionally substituted C₁₋₂₄ alkyl, optionally substitutedC₃₋₈ cycloalkyl, optionally substituted heterocycle, optionallysubstituted C₅₋₂₄ aryl or optionally substituted C₃₋₈ cycloalkenyl;R²⁸ is H, optionally substituted C₁₋₂₄ alkyl, optionally substitutedC₃₋₈ cycloalkyl, optionally substituted heterocycle, optionallysubstituted C₅₋₂₄ aryl or optionally substituted C₃₋₈ cycloalkenyl;R²⁹ is hydrogen, optionally substituted C₁₋₂₄ alkyl, OR²⁶, —NR²⁷R²⁸,optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R³⁰ is optionally substituted C₁₋₂₄ alkyl, optionally substituted C₃₋₈cycloalkyl, optionally substituted heterocycle, optionally substitutedC₅₋₂₄ aryl or optionally substituted C₃₋₈ cycloalkenyl;R³¹ is hydrogen, optionally substituted C₁₋₂₄ alkyl, optionallysubstituted C₃₋₈ cycloalkyl, optionally substituted heterocycle,optionally substituted C₅₋₂₄ aryl or optionally substituted C₃₋₈cycloalkenyl;R³² is hydrogen, optionally substituted C₁₋₂₄ alkyl, optionallysubstituted C₃₋₈ cycloalkyl, optionally substituted heterocycle,optionally substituted C₅₋₂₄ aryl or optionally substituted C₃₋₈cycloalkenyl;R³³ is hydrogen, optionally substituted C₁₋₂₄ alkyl, optionallysubstituted C₃₋₈ cycloalkyl, optionally substituted heterocycle,optionally substituted C₅₋₂₄ aryl or optionally substituted C₃₋₈cycloalkenyl; and m is 1 or 2.

In another embodiment, the invention provides a catalyst represented byFormula (I) wherein:

X is O or S; Y is O or S; Z is N or CR³²; W is O, NR³³ or S;

R¹ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R² is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl, optionally substitutedC₃₋₈ cycloalkenyl or together with R³ may form a polycyclic ring;R³ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl or together with R² may form a polycyclic ring;R⁴ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R⁵ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R⁶ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R⁷ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R⁸ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R⁹ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R¹⁰ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R¹¹ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R¹² is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R¹³ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R¹⁴ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R¹⁵ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R¹⁶ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R¹⁷ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl, or together with R¹⁸ may form a polycyclic ring;R¹⁸ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl, or together with R¹⁷ may form a polycyclic ring;R¹⁹ is hydrogen, optionally substituted C₁₋₂₄ alkyl, —C(O)R²⁵,optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R²⁰ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R²¹ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R²² is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R²³ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R²⁴ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R²⁵ is OH, OR³⁰, NR²⁷R²⁸, optionally substituted C₁₋₂₄ alkyl, optionallysubstituted C₃₋₈ cycloalkyl, optionally substituted heterocycle,optionally substituted C₅₋₂₄ aryl or optionally substituted C₃₋₈cycloalkenyl,R²⁶ is H, optionally substituted C₁₋₂₄ alkyl, optionally substitutedC₃₋₈ cycloalkyl, optionally substituted heterocycle, optionallysubstituted C₅₋₂₄ aryl or optionally substituted C₃₋₈ cycloalkenyl;R²⁷ is H, optionally substituted C₁₋₂₄ alkyl, optionally substitutedC₃₋₈ cycloalkyl, optionally substituted heterocycle, optionallysubstituted C₅₋₂₄ aryl or optionally substituted C₃₋₈ cycloalkenyl;R²⁸ is H, optionally substituted C₁₋₈ alkyl, optionally substituted C₃₋₈cycloalkyl, optionally substituted heterocycle, optionally substitutedC₅₋₂₄ aryl or optionally substituted C₃₋₈ cycloalkenyl;R²⁹ is hydrogen, optionally substituted C₁₋₂₄ alkyl, OR²⁶, —NR²⁷R²⁸,optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R³⁰ is optionally substituted C₁₋₂₄ alkyl, optionally substituted C₃₋₈cycloalkyl, optionally substituted heterocycle, optionally substitutedC₅₋₂₄ aryl or optionally substituted C₃₋₈ cycloalkenyl;R³¹ is hydrogen, optionally substituted C₁₋₂₄ alkyl, optionallysubstituted C₃₋₈ cycloalkyl, optionally substituted heterocycle,optionally substituted C₅₋₂₄ aryl or optionally substituted C₃₋₈cycloalkenyl;R³² is hydrogen, optionally substituted C₁₋₂₄ alkyl, optionallysubstituted C₃₋₈ cycloalkyl, optionally substituted heterocycle,optionally substituted C₅₋₂₄ aryl or optionally substituted C₃₋₈cycloalkenyl;R³³ is hydrogen, optionally substituted C₁₋₂₄ alkyl, optionallysubstituted C₃₋₈ cycloalkyl, optionally substituted heterocycle,optionally substituted C₅₋₂₄ aryl or optionally substituted C₃₋₈cycloalkenyl; and m is 1 or 2.

In another embodiment, the invention provides a catalyst represented byFormula (I) wherein:

X is S; Y is S; Z is N or CR³²; W is O;

R¹ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R² is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl, optionally substitutedC₃₋₈ cycloalkenyl or together with R³ may form a polycyclic ring;R³ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl or together with R² may form a polycyclic ring;R⁴ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R⁵ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R⁶ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R⁷ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R⁸ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R⁹ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R¹⁰ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R¹¹ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R¹² is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R¹³ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R¹⁴ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R¹⁵ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl, or together with R¹⁶ may form an optionallysubstituted polycyclic ring;R¹⁶ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl, or together with R¹⁵ may form an optionallysubstituted polycyclic ring;R¹⁷ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl, or together with R¹⁸ may form an optionallysubstituted polycyclic ring;R¹⁸ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl, or together with R¹⁷ may form an optionallysubstituted polycyclic ring;R¹⁹ is hydrogen, optionally substituted C₁₋₂₄ alkyl, —C(O)R²⁵,optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R²⁰ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R²¹ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R²² is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R²³ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R²⁴ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R²⁵ is OH, OR³⁰, NR²⁷R²⁸, optionally substituted C₁₋₂₄ alkyl, optionallysubstituted C₃₋₈ cycloalkyl, optionally substituted heterocycle,optionally substituted C₅₋₂₄ aryl or optionally substituted C₃₋₈cycloalkenyl,R²⁶ is H, optionally substituted C₁₋₂₄ alkyl, optionally substitutedC₃₋₈ cycloalkyl, optionally substituted heterocycle, optionallysubstituted C₅₋₂₄ aryl or optionally substituted C₃₋₈ cycloalkenyl;R²⁷ is H, optionally substituted C₁₋₂₄ alkyl, optionally substitutedC₃₋₈ cycloalkyl, optionally substituted heterocycle, optionallysubstituted C₅₋₂₄ aryl or optionally substituted C₃₋₈ cycloalkenyl;R²⁸ is H, optionally substituted C₁₋₂₄ alkyl, optionally substitutedC₃₋₈ cycloalkyl, optionally substituted heterocycle, optionallysubstituted C₅₋₂₄ aryl or optionally substituted C₃₋₈ cycloalkenyl;R²⁹ is hydrogen, optionally substituted C₁₋₂₄ alkyl, OR²⁶, —NR²⁷R²⁸,optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R³⁰ is optionally substituted C₁₋₂₄ alkyl, optionally substituted C₃₋₈cycloalkyl, optionally substituted heterocycle, optionally substitutedC₅₋₂₄ aryl or optionally substituted C₃₋₈ cycloalkenyl;R³¹ is hydrogen, optionally substituted C₁₋₂₄ alkyl, optionallysubstituted C₃₋₈ cycloalkyl, optionally substituted heterocycle,optionally substituted C₅₋₂₄ aryl or optionally substituted C₃₋₈cycloalkenyl;R³² is hydrogen, optionally substituted C₁₋₂₄ alkyl, optionallysubstituted C₃₋₈ cycloalkyl, optionally substituted heterocycle,optionally substituted C₅₋₂₄ aryl or optionally substituted C₃₋₈cycloalkenyl; and m is 1 or 2.

In another embodiment, the invention provides a catalyst represented byFormula (I) wherein:

X is S; Y is S; Z is N; W is O;

R¹ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R² is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl, optionally substitutedC₃₋₈ cycloalkenyl or together with R³ may form a polycyclic ring;R³ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl or together with R² may form a polycyclic ring;R⁴ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R⁵ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R⁶ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R⁷ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R⁸ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R⁹ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R¹⁰ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R¹¹ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R¹² is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R¹³ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R¹⁴ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R¹⁵ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl, or together with R¹⁶ may form an optionallysubstituted polycyclic ring;R¹⁶ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl, or together with R¹⁵ may form an optionallysubstituted polycyclic ring;R¹⁷ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl, or together with R¹⁸ may form an optionallysubstituted polycyclic ring;R¹⁸ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl, or together with R¹⁷ may form an optionallysubstituted polycyclic ring;R¹⁹ is hydrogen, optionally substituted C₁₋₂₄ alkyl, —C(O)R²⁵,optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R²⁰ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R²¹ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R²² is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R²³ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R²⁴ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R²⁵ is OH, OR³⁰, NR²⁷R²⁸, optionally substituted C₁₋₂₄ alkyl, optionallysubstituted C₃₋₈ cycloalkyl, optionally substituted heterocycle,optionally substituted C₅₋₂₄ aryl or optionally substituted C₃₋₈cycloalkenyl,R²⁶ is H, optionally substituted C₁₋₂₄ alkyl, optionally substitutedC₃₋₈ cycloalkyl, optionally substituted heterocycle, optionallysubstituted C₅₋₂₄ aryl or optionally substituted C₃₋₈ cycloalkenyl;R²⁷ is H, optionally substituted C₁₋₂₄ alkyl, optionally substitutedC₃₋₈ cycloalkyl, optionally substituted heterocycle, optionallysubstituted C₅₋₂₄ aryl or optionally substituted C₃₋₈ cycloalkenyl;R²⁸ is H, optionally substituted C₁₋₂₄ alkyl, optionally substitutedC₃₋₈ cycloalkyl, optionally substituted heterocycle, optionallysubstituted C₅₋₂₄ aryl or optionally substituted C₃₋₈ cycloalkenyl;R²⁹ is hydrogen, optionally substituted C₁₋₂₄ alkyl, OR²⁶, —NR²⁷R²⁸,optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R³⁰ is optionally substituted C₁₋₂₄ alkyl, optionally substituted C₃₋₈cycloalkyl, optionally substituted heterocycle, optionally substitutedC₅₋₂₄ aryl or optionally substituted C₃₋₈ cycloalkenyl;R³¹ is hydrogen, optionally substituted C₁₋₂₄ alkyl, optionallysubstituted C₃₋₈ cycloalkyl, optionally substituted heterocycle,optionally substituted C₅₋₂₄ aryl or optionally substituted C₃₋₈cycloalkenyl;R³² is hydrogen, optionally substituted C₁₋₂₄ alkyl, optionallysubstituted C₃₋₈ cycloalkyl, optionally substituted heterocycle,optionally substituted C₅₋₂₄ aryl or optionally substituted C₃₋₈cycloalkenyl; and m is 1 or 2.

In one embodiment, the invention provides a catalyst represented byFormula (I) wherein:

X is S; Y is S; Z is CR³²; W is O;

R¹ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R² is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl, optionally substitutedC₃₋₈ cycloalkenyl or together with R³ may form a polycyclic ring;R³ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl or together with R² may form a polycyclic ring;R⁴ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R⁵ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R⁶ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R⁷ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R⁸ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R⁹ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R¹⁰ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R¹¹ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R¹² is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R¹³ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R¹⁴ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R¹⁵ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl, or together with R¹⁶ may form an optionallysubstituted polycyclic ring;R¹⁶ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl, or together with R¹⁵ may form an optionallysubstituted polycyclic ring;R¹⁷ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl, or together with R¹⁸ may form an optionallysubstituted polycyclic ring;R¹⁸ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl, or together with R¹⁷ may form an optionallysubstituted polycyclic ring;R¹⁹ is hydrogen, optionally substituted C₁₋₂₄ alkyl, —C(O)R²⁵,optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R²⁰ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R²¹ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R²² is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R²³ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R²⁴ is hydrogen, optionally substituted C₁₋₂₄ alkyl, halogen, —C(O)R²⁵,—OR²⁶, CN, —NR²⁷R²⁸, NO₂, —CF₃, —S(O)_(m)R²⁹, —P(O)(OH)₂, —OP(O)(OH)₂,—SR³¹, optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R²⁵ is OH, OR³⁰, NR²⁷R²⁸, optionally substituted C₁₋₂₄ alkyl, optionallysubstituted C₃₋₈ cycloalkyl, optionally substituted heterocycle,optionally substituted C₅₋₂₄ aryl or optionally substituted C₃₋₈cycloalkenyl,R²⁶ is H, optionally substituted C₁₋₂₄ alkyl, optionally substitutedC₃₋₈ cycloalkyl, optionally substituted heterocycle, optionallysubstituted C₅₋₂₄ aryl or optionally substituted C₃₋₈ cycloalkenyl;R²⁷ is H, optionally substituted C₁₋₂₄ alkyl, optionally substitutedC₃₋₈ cycloalkyl, optionally substituted heterocycle, optionallysubstituted C₅₋₂₄ aryl or optionally substituted C₃₋₈ cycloalkenyl;R²⁸ is H, optionally substituted C₁₋₂₄ alkyl, optionally substitutedC₃₋₈ cycloalkyl, optionally substituted heterocycle, optionallysubstituted C₅₋₂₄ aryl or optionally substituted C₃₋₈ cycloalkenyl;R²⁹ is hydrogen, optionally substituted C₁₋₂₄ alkyl, OR²⁶, —NR²⁷R²⁸,optionally substituted heterocycle, optionally substituted C₃₋₈cycloalkyl, optionally substituted C₅₋₂₄ aryl or optionally substitutedC₃₋₈ cycloalkenyl;R³⁰ is optionally substituted C₁₋₂₄ alkyl, optionally substituted C₃₋₈cycloalkyl, optionally substituted heterocycle, optionally substitutedC₅₋₂₄ aryl or optionally substituted C₃₋₈ cycloalkenyl;R³¹ is hydrogen, optionally substituted C₁₋₂₄ alkyl, optionallysubstituted C₃₋₈ cycloalkyl, optionally substituted heterocycle,optionally substituted C₅₋₂₄ aryl or optionally substituted C₃₋₈cycloalkenyl;R³² is hydrogen, optionally substituted C₁₋₂₄ alkyl, optionallysubstituted C₃₋₈ cycloalkyl, optionally substituted heterocycle,optionally substituted C₅₋₂₄ aryl or optionally substituted C₃₋₈cycloalkenyl; and m is 1 or 2.

In one embodiment, the invention provides a catalyst represented byFormula (I) wherein: X is S; Y is S; Z is N; W is O; R¹ is hydrogen oroptionally substituted C₁₋₈ alkyl; R² is hydrogen or optionallysubstituted C₁₋₈ alkyl; R³ is hydrogen or optionally substituted C₁₋₈alkyl; R⁴ is hydrogen or optionally substituted C₁₋₈ alkyl; R⁵ ishydrogen, optionally substituted C₁₋₈ alkyl or halogen; R⁶ is hydrogen,optionally substituted C₁₋₈ alkyl or halogen; R⁷ is hydrogen, optionallysubstituted C₁₋₈ alkyl or halogen; R⁸ is hydrogen, optionallysubstituted C₁₋₈ alkyl or halogen; R⁹ is hydrogen, optionallysubstituted C₁₋₈ alkyl or halogen; R¹⁰ is hydrogen, optionallysubstituted C₁₋₈ alkyl or halogen; R¹¹ is hydrogen, optionallysubstituted C₁₋₈ alkyl or halogen; R¹² is hydrogen, optionallysubstituted C₁₋₈ alkyl or halogen; R¹³ is hydrogen, optionallysubstituted C₁₋₈ alkyl or halogen; R¹⁴ is hydrogen, optionallysubstituted C₁₋₈ alkyl or halogen; R¹⁵ is hydrogen, optionallysubstituted C₁₋₈ alkyl or halogen, or together with R¹⁶ may form anoptionally substituted polycyclic ring; R¹⁶ is hydrogen, optionallysubstituted C₁₋₈ alkyl or halogen, or together with R¹⁵ may form anoptionally substituted polycyclic ring; R¹⁷ is hydrogen, optionallysubstituted C₁₋₈ alkyl, halogen, or together with R¹⁸ may form anoptionally substituted polycyclic ring; R¹⁸ is hydrogen, optionallysubstituted C₆₋₁₀ aryl, optionally substituted C₁₋₈ alkyl, halogen, ortogether with R¹⁷ may form an optionally substituted polycyclic ring;R¹⁹ is optionally substituted C₁₋₈ alkyl; R²⁰ is hydrogen or optionallysubstituted C₆₋₁₀ aryl; R²¹ is hydrogen; R²² is hydrogen; R²³ ishydrogen; and R²⁴ is hydrogen.

In one embodiment, the invention provides a catalyst represented byFormula (I) wherein: X is S; Y is S; Z is N; W is O; R¹ is hydrogen oroptionally substituted C₁₋₈ alkyl; R² is hydrogen or optionallysubstituted C₁₋₈ alkyl; R³ is hydrogen; R⁴ is hydrogen; R⁵ is hydrogen,optionally substituted C₁₋₈ alkyl or halogen; R⁶ is hydrogen oroptionally substituted C₁₋₈ alkyl; R⁷ is hydrogen, optionallysubstituted C₁₋₈ alkyl or halogen; R⁸ is hydrogen or optionallysubstituted C₁₋₈ alkyl; R⁹ is hydrogen, optionally substituted C₁₋₈alkyl or halogen; R¹⁰ is hydrogen, optionally substituted C₁₋₈ alkyl orhalogen; R¹¹ is hydrogen or optionally substituted C₁₋₈ alkyl; R¹² ishydrogen, optionally substituted C₁₋₈ alkyl or halogen; R¹³ is hydrogenor optionally substituted C₁₋₈ alkyl; R¹⁴ is hydrogen, optionallysubstituted C₁₋₈ alkyl or halogen; R¹⁵ is hydrogen or halogen; R¹⁶ ishydrogen; R¹⁷ is hydrogen or together with R¹⁸ may form a polycyclicring; R¹⁸ is optionally substituted C₆₋₁₀ aryl, halogen or together withR¹⁷ may form a polycyclic ring; R¹⁹ is optionally substituted C₁₋₈alkyl; R²⁰ is hydrogen or optionally substituted C₆₋₁₀ aryl; R²¹ ishydrogen; R²² is hydrogen; R²³ is hydrogen; and R²⁴ is hydrogen.

In one embodiment, the invention provides a catalyst represented byFormula (I) wherein: X is S; Y is S; Z is N; W is O; R¹ is hydrogen oroptionally substituted C₁₋₈ alkyl; R² is hydrogen or optionallysubstituted C₁₋₈ alkyl; R³ is hydrogen; R⁴ is hydrogen; R⁵ is hydrogen,optionally substituted C₁₋₈ alkyl or halogen; R⁶ is hydrogen oroptionally substituted C₁₋₈ alkyl; R⁷ is hydrogen, optionallysubstituted C₁₋₈ alkyl or halogen; R⁸ is hydrogen or optionallysubstituted C₁₋₈ alkyl; R⁹ is hydrogen, optionally substituted C₁₋₈alkyl or halogen; R¹⁰ is hydrogen, optionally substituted C₁₋₈ alkyl orhalogen; R¹¹ is hydrogen or optionally substituted C₁₋₈ alkyl; R¹² ishydrogen, optionally substituted C₁₋₈ alkyl or halogen; R¹³ is hydrogenor optionally substituted C₁₋₈ alkyl; R¹⁴ is hydrogen, optionallysubstituted C₁₋₈ alkyl or halogen; R¹⁵ is hydrogen or halogen, ortogether with R¹⁶ may form an optionally substituted polycyclic ring;R¹⁶ is hydrogen, or together with R¹⁵ may form an optionally substitutedpolycyclic ring; R¹⁷ is hydrogen or together with R¹⁸ may form anoptionally substituted polycyclic ring; R¹⁸ is optionally substitutedC₆₋₁₀ aryl, halogen or together with R¹⁷ may form an optionallysubstituted polycyclic ring; R¹⁹ is optionally substituted C₁₋₈ alkyl;R²⁰ is hydrogen or optionally substituted C₆₋₁₀ aryl; R²¹ is hydrogen;R²² is hydrogen; R²³ is hydrogen; and R²⁴ is hydrogen.

In one embodiment, the invention provides a catalyst represented byFormula (I) wherein: X is S; Y is S; Z is N; W is O; R¹ is hydrogen; R²is hydrogen; R³ is hydrogen; R⁴ is hydrogen; R⁵ is hydrogen, halogen oroptionally substituted C₁₋₈ alkyl; R⁶ is hydrogen or optionallysubstituted C₁₋₈ alkyl; R⁷ is hydrogen or optionally substituted C₁₋₈alkyl; R⁸ is hydrogen or optionally substituted C₁₋₈ alkyl; R⁹ ishydrogen, halogen or optionally substituted C₁₋₈ alkyl; R¹⁰ is hydrogen,halogen or optionally substituted C₁₋₈ alkyl; R¹¹ is hydrogen oroptionally substituted C₁₋₈ alkyl; R¹² is hydrogen or optionallysubstituted C₁₋₈ alkyl; R¹³ is hydrogen or optionally substituted C₁₋₈alkyl; R¹⁴ is hydrogen, halogen or optionally substituted C₁₋₈ alkyl;R¹⁵ is hydrogen or halogen, or together with R¹⁶ may form an optionallysubstituted polycyclic ring; R¹⁶ is hydrogen, or together with R¹⁵ mayform an optionally substituted polycyclic ring; R¹⁷ is hydrogen ortogether with R¹⁸ may form an optionally substituted polycyclic ring;R¹⁸ is optionally substituted C₆₋₁₀ aryl, halogen, or together with R¹⁷may form an optionally substituted polycyclic ring; R¹⁹ is optionallysubstituted C₁₋₈ alkyl; R²⁰ is hydrogen or optionally substituted C₆₋₁₀aryl; R²¹ is hydrogen; R²² is hydrogen; R²³ is hydrogen; and R²⁴ ishydrogen.

In one embodiment, the invention provides a catalyst represented byFormula (I) wherein: X is S; Y is S; Z is N; W is O; R¹ is optionallysubstituted C₁₋₈ alkyl; R² is optionally substituted C₁₋₈ alkyl; R³ ishydrogen; R⁴ is hydrogen; R⁵ is halogen; R⁶ is hydrogen; R⁷ is halogen;R⁸ is hydrogen; R⁹ is halogen; R¹⁰ is halogen; R¹¹ is hydrogen; R¹² ishydrogen or halogen; R¹³ is hydrogen; R¹⁴ is halogen; R¹⁵ is halogen;R¹⁶ is hydrogen; R¹⁷ is hydrogen or together with R¹⁸ forms anoptionally substituted naphtyl or phenantryl ring; R¹⁸ is halogen ortogether with R¹⁷ forms an optionally substituted naphtyl or phenantrylring; R¹⁹ is optionally substituted C₁₋₈ alkyl; R²⁰ is hydrogen; R²¹ ishydrogen; R²² is hydrogen; R²³ is hydrogen; and R²⁴ is hydrogen.

In one embodiment, the invention provides a catalyst represented byFormula (I) wherein: X is S; Y is S; Z is N; W is O; R¹ is hydrogen; R²is hydrogen; R³ is hydrogen; R⁴ is hydrogen; R⁵ is hydrogen, F, methylor i-Pr; R⁶ is hydrogen or t-Bu; R⁷ is hydrogen or methyl; R⁸ ishydrogen or t-Bu; R⁹ is hydrogen, F, methyl or i-Pr; R¹⁰ is hydrogen, F,methyl or i-Pr; R¹¹ is hydrogen or t-Bu; R¹² is hydrogen or methyl; R¹³is hydrogen or t-Bu; R¹⁴ is F, methyl, i-Pr or hydrogen; R¹⁵ ishydrogen, methyl or Cl, or together with R¹⁶ forms 2-phenyl-naphthyl orphenanthryl; R¹⁶ is hydrogen, or together with R¹⁵ forms2-phenyl-naphthyl or phenanthryl; R¹⁷ is hydrogen or together with R¹⁸forms 2-phenyl-naphthyl, phenanthryl, or methylphenantryl; R¹⁸ is Cl,3,5-dichloro-phenyl, phenyl, t-Bu or together with R¹⁷ forms2-phenyl-naphthyl, phenanthryl or methylphenantryl; R¹⁹ is i-Pr; R²⁰ ishydrogen or phenyl; R²¹ is hydrogen; R²² is hydrogen; R²³ is hydrogen;and R²⁴ is hydrogen.

In one embodiment, the invention provides a catalyst represented byFormula (I) wherein: X is S; Y is S; Z is N; W is O; R¹ is methyl; R² ismethyl; R³ is hydrogen; R⁴ is hydrogen; R⁵ is F; R⁶ is hydrogen; R⁷ ishydrogen or F; R⁸ is hydrogen; R⁹ is F; R¹⁰ is F; R¹¹ is hydrogen; R¹²is hydrogen or F; R¹³ is hydrogen; R¹⁴ is F; R¹⁵ is Cl; R¹⁶ is hydrogen;R¹⁷ is hydrogen or together with R¹⁸ forms naphtyl or phenanthryl; R¹⁸is hydrogen, Cl, or together with R¹⁷ forms naphtyl or phenanthryl; R¹⁹is i-Pr; R²⁰ is hydrogen; R²¹ is hydrogen; R²² is hydrogen; R²³ ishydrogen; and R²⁴ is hydrogen.

In one embodiment, the invention provides a catalyst represented byFormula (I) wherein: X is S; Y is S; Z is N; W is O; R¹ is Me; R² is Me;R³ is hydrogen; R⁴ is hydrogen; R⁵ is Me or F; R⁶ is hydrogen; R⁷ ishydrogen or F; R⁸ is hydrogen; R⁹ is hydrogen or F; R¹⁰ is Me or F; R¹¹is hydrogen; R¹² is hydrogen or F; R¹³ is hydrogen; R¹⁴ is hydrogen orF; R¹⁵ is hydrogen or Cl; R¹⁶ is hydrogen; R¹⁷ is hydrogen or togetherwith R¹⁸ forms naphthyl or phenantryl; R¹⁸ is Cl, phenyl or togetherwith R¹⁷ forms naphthyl or phenantryl; R¹⁹ is i-Pr; R²⁰ is hydrogen; R²¹is hydrogen; R²² is hydrogen; R²³ is hydrogen; and R²⁴ is hydrogen.

In one embodiment, the invention provides a catalyst represented byFormula (I) wherein: X is S; Y is S; Z is N; W is O; R¹ is hydrogen; R²is hydrogen; R³ is hydrogen; R⁴ is hydrogen; R⁵ is Me, F or i-Pr; R⁶ ishydrogen or t-Bu; R⁷ is hydrogen or Me; R⁸ is hydrogen or t-Bu; R⁹ ishydrogen, Me, t-Bu, F or i-Pr; R¹⁰ is hydrogen, Me, F or i-Pr; R¹¹ ishydrogen or t-Bu; R¹² is hydrogen or Me; R¹³ is hydrogen or t-Bu; R¹⁴ ishydrogen, Me, F or i-Pr; R¹⁵ is hydrogen, methyl or Cl, or together withR¹⁶ forms 2-phenyl-naphthyl or phenanthryl; R¹⁶ is hydrogen, or togetherwith R¹⁵ forms 2-phenyl-naphthyl or phenanthryl; R¹⁷ is hydrogen ortogether with R¹⁸ forms 2-phenyl-naphthyl, naphtyl, phenanthryl, ormethylphenantryl; R¹⁸ is Cl, 3,5-dichloro-phenyl, phenyl, t-Bu ortogether with R¹⁷ forms 2-phenyl-naphthyl, naphtyl, phenanthryl ormethylphenantryl; R¹⁵ is hydrogen or Cl; R¹⁶ is hydrogen; R¹⁷ ishydrogen or together with R¹⁸ form an optionally substituted naphthyl oran optionally substituted phenanthryl ring; R¹⁸ is Cl, phenyl ortogether with R¹⁷ form an optionally substituted naphthyl or anoptionally substituted phenanthryl ring; R¹⁹ is i-Pr; R²⁰ is hydrogen isphenyl; R²¹ is hydrogen; R²² is hydrogen; R²³ is hydrogen; and R²⁴ ishydrogen.

In one embodiment, the invention provides a compound wherein the moiety

of Formula (I) is

In one embodiment, the invention provides a compound wherein the moiety

of Formula (I) is

In one embodiment, the invention provides a compound wherein the moiety

of Formula (I) is

In one embodiment, the invention provides a compound of Formula (I) isselected from:

In one embodiment, a compound of Formula (I) is an olefin metathesiscatalyst. In one embodiment, a compound of Formula (I) is a Z-selectiveolefin metathesis catalyst.

In one embodiment, a compound of Formula (I) is an olefin metathesiscatalyst. In one embodiment, a compound of Formula (I) is an E-selectiveolefin metathesis catalyst.

Olefin Reactants

In one embodiment, an olefin reactant comprises a reactant internalolefin, wherein the reactant internal olefin is in a Z-configuration.

In one embodiment, an olefin reactant comprises a reactant internalolefin, wherein the reactant internal olefin is di-substituted and is ina Z-configuration.

In one embodiment, an olefin reactant comprising a reactant internalolefin is represented by the structure of Formula (1):

wherein,

D¹ and D² are identical or are independently selected from nil, CH₂, O,or S; and

E¹ and E² are identical or are independently selected from hydrogen,hydrocarbyl (e.g., C₁-C₂₀ alkyl, C₅-C₂₀ aryl, C₅-C₃₀ aralkyl, or C₅-C₃₀alkaryl), substituted hydrocarbyl (e.g., substituted C₁-C₂₀ alkyl,C₅-C₂₀ aryl, C₅-C₃₀ aralkyl, or C₅-C₃₀ alkaryl), heteroatom-containinghydrocarbyl (e.g., C₁-C₂₀ heteroalkyl, C₅-C₂₀ heteroaryl,heteroatom-containing C₅-C₃₀ aralkyl, or heteroatom-containing C₅-C₃₀alkaryl), and substituted heteroatom-containing hydrocarbyl (e.g.,substituted C₁-C₂₀ heteroalkyl, C₅-C₂₀ heteroaryl, heteroatom-containingC₅-C₃₀ aralkyl, or heteroatom-containing C₅-C₃₀ alkaryl) and, ifsubstituted hydrocarbyl or substituted heteroatom-containinghydrocarbyl, wherein the substituents may be functional groups (“Fn”)such as halo, hydroxyl, sulfhydryl, C₁-C₂₄ alkoxy, C₅-C₂₄ aryloxy,C₆-C₂₄ aralkyloxy, C₆-C₂₄ alkaryloxy, acyl (including C₂-C₂₄alkylcarbonyl (—CO-alkyl) and C₆-C₂₄ arylcarbonyl (—CO-aryl)), acyloxy(—O-acyl, including C₂-C₂₄ alkylcarbonyloxy (—O—CO-alkyl) and C₆-C₂₄arylcarbonyloxy (—O—CO-aryl)), C₂-C₂₄ alkoxycarbonyl (—(CO)—O-alkyl),C₆-C₂₄ aryloxycarbonyl (—(CO)—O-aryl), halocarbonyl (—CO)—X where X ishalo), C₂-C₂₄ alkylcarbonato (—O—(CO)—O-alkyl), C₆-C₂₄ arylcarbonato(—O—(CO)—O-aryl), carboxy (—COOH), carboxylato (—COO⁻), carbamoyl(—(CO)—NH₂), mono-(C₁-C₂₄ alkyl)-substituted carbamoyl (—(CO)—NH(C₁-C₂₄alkyl)), di-(C₁-C₂₄ alkyl)-substituted carbamoyl (—(CO)—N(C₁-C₂₄alkyl)₂), mono-(C₁-C₂₄ haloalkyl)-substituted carbamoyl (—(CO)—NH(C₁-C₂₄haloalkyl)), di-(C₁-C₂₄ haloalkyl)-substituted carbamoyl (—(CO)—N(C₁-C₂₄haloalkyl)₂), mono-(C₅-C₂₄ aryl)-substituted carbamoyl (—(CO)—NH-aryl),di-(C₅-C₂₄ aryl)-substituted carbamoyl (—(CO)—N(C₅-C₂₄ aryl)₂),di-N—(C₁-C₂₄ alkyl), N—(C₅-C₂₄ aryl)-substituted carbamoyl(—(CO)—N(C₁-C₂₄ alkyl)(C₅-C₂₄ aryl), thiocarbamoyl (—(CS)—NH₂),mono-(C₁-C₂₄ alkyl)-substituted thiocarbamoyl (—(CS)—NH(C₁-C₂₄ alkyl)),di-(C₁-C₂₄ alkyl)-substituted thiocarbamoyl (—(CS)—N(C₁-C₂₄ alkyl)₂),mono-(C₅-C₂₄ aryl)-substituted thiocarbamoyl (—(CS)—NH-aryl), di-(C₅-C₂₄aryl)-substituted thiocarbamoyl (—(CS)—N(C₅-C₂₄ aryl)₂), di-N—(C₁-C₂₄alkyl), N—(C₅-C₂₄ aryl)-substituted thiocarbamoyl (—(CS)—N(C₁-C₂₄alkyl)(C₅-C₂₄ aryl), carbamido (—NH—(CO)—NH₂), cyano (—C≡N), cyanato(—O—C≡N), thiocyanato (—S—C≡N), isocyanate (—NisCisO), thioisocyanate(—NisCisS), formyl (—(CO)—H), thioformyl (—(CS)—H), amino (—NH₂),mono-(C₁-C₂₄ alkyl)-substituted amino (—NH(C₁-C₂₄ alkyl), di-(C₁-C₂₄alkyl)-substituted amino (—N(C₁-C₂₄ alkyl)₂), mono-(C₅-C₂₄aryl)-substituted amino (—NH(C₅-C₂₄ aryl), di-(C₅-C₂₄ aryl)-substitutedamino (—N(C₅-C₂₄ aryl)₂), C₂-C₂₄ alkylamido (—NH—(CO)-alkyl), C₆-C₂₄arylamido (—NH—(CO)-aryl), imino (-CRisNH where R includes withoutlimitation hydrogen, C₁-C₂₄ alkyl, C₅-C₂₄ aryl, C₆-C₂₄ alkaryl, C₆-C₂₄aralkyl, etc.), C₂-C₂₀ alkylimino (-CRisN(alkyl), where R includeswithout limitation hydrogen, C₁-C₂₄ alkyl, C₅-C₂₄ aryl, C₆-C₂₄ alkaryl,C₆-C₂₄ aralkyl, etc.), arylimino (-CRisN(aryl), where R includes withoutlimitation hydrogen, C₁-C₂₀ alkyl, C₅-C₂₄ aryl, C₆-C₂₄ alkaryl, C₆-C₂₄aralkyl, etc.), nitro (—NO₂), nitroso (—NO), sulfo (—SO₂—OH), sulfonato(—SO₂—O—), C₁-C₂₄ alkylsulfanyl (—S-alkyl; also termed “alkylthio”),C₅-C₂₄ arylsulfanyl (—S-aryl; also termed “arylthio”), C₁-C₂₄alkylsulfinyl (—(SO)-alkyl), C₅-C₂₄ arylsulfinyl (—(SO)-aryl), C₁-C₂₄alkylsulfonyl (—SO₀₂-alkyl), C₁-C₂₄ monoalkylaminosulfonyl (—SO₂—N(H)alkyl), C₁-C₂₄ dialkylaminosulfonyl (—SO₂—N(alkyl)₂), C₅-C₂₄arylsulfonyl (—SO₀₂-aryl), boryl (—BH₂), borono (—B(OH)₂), boronato(—B(OR)₂ where R is alkyl or aryl), phosphono (—P(O)(OH)₂), phosphonato(—P(O)(O—)₂), phosphinato (—P(O)(O—)), phospho (—PO₂), and phosphino(—PH₂); and the hydrocarbyl moieties C₁-C₂₄ alkyl (preferably C₁-C₁₂alkyl, more preferably C₁-C₆ alkyl), C₅-C₂₄ aryl (preferably C₅-C₁₄aryl), C₆-C₂₄ alkaryl (preferably C₆-C₁₆ alkaryl), and C₆-C₂₄ aralkyl(preferably C₆-C₁₆ aralkyl), with the proviso that if E¹ is hydrogen,then D¹ cannot be nil; and where if E² is hydrogen, then D² cannot benil.

In one embodiment, there is a first internal olefin reactant and asecond internal olefin reactant, where the first internal olefinreactant and the second internal olefin reactant may be the same ordifferent, wherein the first internal olefin reactant and the secondinternal olefin reactant are each in a Z-configuration.

In one embodiment, there is a first internal olefin reactant and asecond internal olefin reactant, where the first internal olefinreactant and the second internal olefin reactant may be the same ordifferent, wherein the first olefin reactant and the second olefinreactant each comprise a reactant internal olefin.

In one embodiment, there is a first internal olefin reactant and asecond internal olefin reactant, where the first internal olefinreactant and the second internal olefin reactant may be the same ordifferent, wherein the first internal olefin reactant and the secondinternal olefin reactant each comprise a reactant internal olefin,wherein the reactant internal olefin is di-substituted and in aZ-configuration.

In one embodiment, there is a first internal olefin reactant and asecond internal olefin reactant, where the first internal olefinreactant is of Formula (1) and the second internal olefin reactant is ofFormula (1), wherein the first internal olefin reactant and the secondinternal olefin reactant may be the same or different.

In one embodiment, an olefin reactant comprises a reactant internalolefin, wherein the reactant internal olefin is in an E-configuration.

In one embodiment, an olefin reactant comprises a reactant internalolefin, wherein the reactant internal olefin is di-substituted and is inan E-configuration.

In one embodiment, an olefin reactant comprising a reactant internalolefin is represented by the structure of Formula (2):

wherein

D¹³ and D¹⁴ are identical or are independently selected from nil, CH₂,O, or S; and

E¹³ and E¹⁴ are identical or are independently selected from hydrogen,hydrocarbyl (e.g., C₁-C₂₀ alkyl, C₅-C₂₀ aryl, C₅-C₃₀ aralkyl, or C₅-C₃₀alkaryl), substituted hydrocarbyl (e.g., substituted C₁-C₂₀ alkyl,C₅-C₂₀ aryl, C₅-C₃₀ aralkyl, or C₅-C₃₀ alkaryl), heteroatom-containinghydrocarbyl (e.g., C₁-C₂₀ heteroalkyl, C₅-C₂₀ heteroaryl,heteroatom-containing C₅-C₃₀ aralkyl, or heteroatom-containing C₅-C₃₀alkaryl), and substituted heteroatom-containing hydrocarbyl (e.g.,substituted C₁-C₂₀ heteroalkyl, C₅-C₂₀ heteroaryl, heteroatom-containingC₅-C₃₀ aralkyl, or heteroatom-containing C₅-C₃₀ alkaryl) and, ifsubstituted hydrocarbyl or substituted heteroatom-containinghydrocarbyl, wherein the substituents may be functional groups (“Fn”)such as halo, hydroxyl, sulfhydryl, C₁-C₂₄ alkoxy, C₅-C₂₄ aryloxy,C₆-C₂₄ aralkyloxy, C₆-C₂₄ alkaryloxy, acyl (including C₂-C₂₄alkylcarbonyl (—CO-alkyl) and C₆-C₂₄ arylcarbonyl (—CO-aryl)), acyloxy(—O-acyl, including C₂-C₂₄ alkylcarbonyloxy (—O—CO-alkyl) and C₆-C₂₄arylcarbonyloxy (—O—CO-aryl)), C₂-C₂₄ alkoxycarbonyl (—(CO)—O-alkyl),C₆-C₂₄ aryloxycarbonyl (—(CO)—O-aryl), halocarbonyl (—CO)—X where X ishalo), C₂-C₂₄ alkylcarbonato (—O—(CO)—O-alkyl), C₆-C₂₄ arylcarbonato(—O—(CO)—O-aryl), carboxy (—COOH), carboxylato (—COO⁻), carbamoyl(—(CO)—NH₂), mono-(C₁-C₂₄ alkyl)-substituted carbamoyl (—(CO)—NH(C₁-C₂₄alkyl)), di-(C₁-C₂₄ alkyl)-substituted carbamoyl (—(CO)—N(C₁-C₂₄alkyl)₂), mono-(C₁-C₂₄ haloalkyl)-substituted carbamoyl (—(CO)—NH(C₁-C₂₄haloalkyl)), di-(C₁-C₂₄ haloalkyl)-substituted carbamoyl (—(CO)—N(C₁-C₂₄haloalkyl)₂), mono-(C₅-C₂₄ aryl)-substituted carbamoyl (—(CO)—NH-aryl),di-(C₅-C₂₄ aryl)-substituted carbamoyl (—(CO)—N(C₅-C₂₄ aryl)₂),di-N—(C₁-C₂₄ alkyl), N—(C₅-C₂₄ aryl)-substituted carbamoyl(—(CO)—N(C₁-C₂₄ alkyl)(C₅-C₂₄ aryl), thiocarbamoyl (—(CS)—NH₂),mono-(C₁-C₂₄ alkyl)-substituted thiocarbamoyl (—(CS)—NH(C₁-C₂₄ alkyl)),di-(C₁-C₂₄ alkyl)-substituted thiocarbamoyl (—(CS)—N(C₁-C₂₄ alkyl)₂),mono-(C₅-C₂₄ aryl)-substituted thiocarbamoyl (—(CS)—NH-aryl), di-(C₅-C₂₄aryl)-substituted thiocarbamoyl (—(CS)—N(C₅-C₂₄ aryl)₂), di-N—(C₁-C₂₄alkyl), N—(C₅-C₂₄ aryl)-substituted thiocarbamoyl (—(CS)—N(C₁-C₂₄alkyl)(C₅-C₂₄ aryl), carbamido (—NH—(CO)—NH₂), cyano (—C—N), cyanato(—O—C≡N), thiocyanato (—S—C≡N), isocyanate (—N═C═O), thioisocyanate(—N═C═S), formyl (—(CO)—H), thioformyl (—(CS)—H), amino (—NH₂),mono-(C₁-C₂₄ alkyl)-substituted amino (—NH(C₁-C₂₄ alkyl), di-(C₁-C₂₄alkyl)-substituted amino (—N(C₁-C₂₄ alkyl)₂), mono-(C₅-C₂₄aryl)-substituted amino (—NH(C₅-C₂₄ aryl), di-(C₅-C₂₄ aryl)-substitutedamino (—N(C₅-C₂₄ aryl)₂), C₂-C₂₄ alkylamido (—NH—(CO)-alkyl), C₆-C₂₄arylamido (—NH—(CO)-aryl), imino (—CR═NH where R includes withoutlimitation hydrogen, C₁-C₂₄ alkyl, C₅-C₂₄ aryl, C₆-C₂₄ alkaryl, C₆-C₂₄aralkyl, etc.), C₂-C₂₀ alkylimino (—CR═N(alkyl), where R includeswithout limitation hydrogen, C₁-C₂₄ alkyl, C₅-C₂₄ aryl, C₆-C₂₄ alkaryl,C₆-C₂₄ aralkyl, etc.), arylimino (—CR═N(aryl), where R includes withoutlimitation hydrogen, C₁-C₂₀ alkyl, C₅-C₂₄ aryl, C₆-C₂₄ alkaryl, C₆-C₂₄aralkyl, etc.), nitro (—NO₂), nitroso (—NO), sulfo (—SO₂—OH), sulfonato(—SO₂—O—), C₁-C₂₄ alkylsulfanyl (—S-alkyl; also termed “alkylthio”),C₅-C₂₄ arylsulfanyl (—S-aryl; also termed “arylthio”), C₁-C₂₄alkylsulfinyl (—(SO)-alkyl), C₅-C₂₄ arylsulfinyl (—(SO)-aryl), C₁-C₂₄alkylsulfonyl (—SO₂-alkyl), C₁-C₂₄ monoalkylaminosulfonyl (—SO₂—N(H)alkyl), C₁-C₂₄ dialkylaminosulfonyl (—SO₂—N(alkyl)₂), C₅-C₂₄arylsulfonyl (—SO₂-aryl), boryl (—BH₂), borono (—B(OH)₂), boronato(—B(OR)₂ where R is alkyl or aryl), phosphono (—P(O)(OH)₂), phosphonato(—P(O)(O—)₂), phosphinato (—P(O)(O—)), phospho (—PO₂), and phosphino(—PH₂); and the hydrocarbyl moieties C₁-C₂₄ alkyl (preferably C₁-C₁₂alkyl, more preferably C₁-C₆ alkyl), C₅-C₂₄ aryl (preferably C₅-C₁₄aryl), C₆-C₂₄ alkaryl (preferably C₆-C₁₆ alkaryl), and C₆-C₂₄ aralkyl(preferably C₆-C₁₆ aralkyl).

In one embodiment, there is a first internal olefin reactant and asecond internal olefin reactant, where the first internal olefinreactant and the second internal olefin reactant may be the same ordifferent, wherein the first internal olefin reactant and the secondinternal olefin reactant are each in an E-configuration.

In one embodiment, there is a first internal olefin reactant and asecond internal olefin reactant, where the first internal olefinreactant and the second internal olefin reactant may be the same ordifferent, wherein the first internal olefin reactant and the secondinternal olefin reactant each comprise a reactant internal olefin,wherein the reactant internal olefin is di-substituted and is in anE-configuration.

In one embodiment, there is a first internal olefin reactant and asecond internal olefin reactant, where the first internal olefinreactant is of Formula (2) and the second internal olefin reactant is ofFormula (2), wherein the first internal olefin reactant and the secondinternal olefin reactant may be the same or different.

In general the second olefin reactant comprising a terminal olefin maybe represented by the structure of Formula (3):

wherein U^(α) is selected from the group comprising nil, CH₂, O, or Sand T^(α) is selected from the group consisting of hydrogen, hydrocarbyl(e.g., C₁-C₂₀ alkyl, C₅-C₂₀ aryl, C₅-C₃₀ aralkyl, or C₅-C₃₀ alkaryl),substituted hydrocarbyl (e.g., substituted C₁-C₂₀ alkyl, C₅-C₂₀ aryl,C₅-C₃₀ aralkyl, or C₅-C₃₀ alkaryl), heteroatom-containing hydrocarbyl(e.g., C₁-C₂₀ heteroalkyl, C₅-C₂₀ heteroaryl, heteroatom-containingC₅-C₃₀ aralkyl, or heteroatom-containing C₅-C₃₀ alkaryl), andsubstituted heteroatom-containing hydrocarbyl (e.g., substituted C₁-C₂₀heteroalkyl, C₅-C₂₀ heteroaryl, heteroatom-containing C₅-C₃₀ aralkyl, orheteroatom-containing C₅-C₃₀ alkaryl) and, if substituted hydrocarbyl orsubstituted heteroatom-containing hydrocarbyl, wherein the substituentsmay be functional groups (“Fn”) such as phosphonato, phosphoryl,phosphanyl, phosphino, sulfonato, C₁-C₂₀ alkylsulfanyl, C₅-C₂₀arylsulfanyl, C₁-C₂₀ alkylsulfonyl, C₅-C₂₀ arylsulfonyl, C₁-C₂₀alkylsulfinyl, C₅-C₂₀ arylsulfinyl, sulfonamido, amino, amido, imino,nitro, nitroso, hydroxyl, C₁-C₂₀ alkoxy, C₅-C₂₀ aryloxy, C₂-C₂₀alkoxycarbonyl, C₅-C₂₀ aryloxycarbonyl, carboxyl, carboxylato, mercapto,formyl, C₁-C₂₀ thioester, cyano, cyanato, carbamoyl, epoxy, styrenyl,silyl, silyloxy, silanyl, siloxazanyl, boronato, boryl, or halogen, or ametal-containing or metalloid-containing group (wherein the metal maybe, for example, Sn or Ge).

In one embodiment, there is a first internal olefin reactant and asecond terminal olefin reactant, wherein the first internal olefinreactant is in an E-configuration.

In one embodiment, there is a first internal olefin reactant and asecond terminal olefin reactant, wherein the first internal olefinreactant is in a Z-configuration.

In one embodiment, there is a first internal olefin reactant and asecond terminal olefin reactant, where the first internal olefinreactant is of Formula (1) and the second terminal olefin reactant is ofFormula (3).

In one embodiment, there is a first internal olefin reactant and asecond terminal olefin reactant, where the first internal olefinreactant is of Formula (2) and the second terminal olefin reactant is ofFormula (3).

Olefin Products

In one embodiment, the olefin product is at least one cross metathesisproduct, wherein the at least one cross metathesis product is in aZ-configuration.

In one embodiment, the olefin product is at least one cross metathesisproduct, wherein the at least one cross metathesis product isdi-substituted and is in a Z-configuration.

In one embodiment, an at least one cross metathesis product comprises aproduct internal olefin, wherein the product internal olefin is in aZ-configuration.

In one embodiment, an at least one cross metathesis product comprises aproduct internal olefin, wherein the product internal olefin isdi-substituted and is in a Z-configuration.

In one embodiment, the olefin product is at least one cross metathesisproduct, wherein the at least one cross metathesis product is in anE-configuration.

In one embodiment, the olefin product is at least one cross metathesisproduct, wherein the at least one cross metathesis product isdi-substituted and is in an E-configuration.

In one embodiment, an at least one cross metathesis product comprises aproduct internal olefin, wherein the product internal olefin is in anE-configuration.

In one embodiment, an at least one cross metathesis product comprises aproduct internal olefin, wherein the product internal olefin isdi-substituted and is in an E-configuration.

In some embodiments, the invention provides a method that produces acompound (i.e., a product, olefin product; e.g., cross metathesisproduct) having a carbon-carbon double bond (e.g., a product internalolefin) in a Z:E ratio greater than about 1:1, greater than about 2:1,greater than about 3:1, greater than about 4:1, greater than about 5:1,greater than about 6:1, greater than about 7:1, greater than about 8:1,greater than about 9:1, greater than about 95:5, greater than about96:4, greater than about 97:3, greater than about 98:2, or in somecases, greater than about 99:1. In some cases, about 100% of thecarbon-carbon double bond produced in the metathesis reaction may have aZ configuration. The Z or cis selectivity may also be expressed as apercentage of product formed (e.g., cross metathesis product). In somecases, the product (e.g., cross metathesis product) may be greater thanabout 50% Z, greater than about 60% Z, greater than about 70% Z, greaterthan about 80% Z, greater than about 90% Z, greater than about 95% Z,greater than about 96% Z, greater than about 97% Z, greater than about98% Z, greater than about 99% Z, or in some cases greater than about99.5% Z.

In another embodiment, an at least one cross metathesis productcomprising a product internal olefin is represented by the structure ofFormula (4):

wherein,

D³ and D⁴ are identical or are independently selected from nil, CH₂, O,or S; and

E³ and E⁴ are identical or are independently selected from hydrogen,hydrocarbyl (e.g., C₁-C₂₀ alkyl, C₅-C₂₀ aryl, C₅-C₃₀ aralkyl, or C₅-C₃₀alkaryl), substituted hydrocarbyl (e.g., substituted C₁-C₂₀ alkyl,C₅-C₂₀ aryl, C₅-C₃₀ aralkyl, or C₅-C₃₀ alkaryl), heteroatom-containinghydrocarbyl (e.g., C₁-C₂₀ heteroalkyl, C₅-C₂₀ heteroaryl,heteroatom-containing C₅-C₃₀ aralkyl, or heteroatom-containing C₅-C₃₀alkaryl), and substituted heteroatom-containing hydrocarbyl (e.g.,substituted C₁-C₂₀ heteroalkyl, C₅-C₂₀ heteroaryl, heteroatom-containingC₅-C₃₀ aralkyl, or heteroatom-containing C₅-C₃₀ alkaryl) and, ifsubstituted hydrocarbyl or substituted heteroatom-containinghydrocarbyl, wherein the substituents may be functional groups (“Fn”)such as halo, hydroxyl, sulfhydryl, C₁-C₂₄ alkoxy, C₅-C₂₄ aryloxy,C₆-C₂₄ aralkyloxy, C₆-C₂₄ alkaryloxy, acyl (including C₂-C₂₄alkylcarbonyl (—CO-alkyl) and C₆-C₂₄ arylcarbonyl (—CO-aryl)), acyloxy(—O-acyl, including C₂-C₂₄ alkylcarbonyloxy (—O—CO-alkyl) and C₆-C₂₄arylcarbonyloxy (—O—CO-aryl)), C₂-C₂₄ alkoxycarbonyl (—(CO)—O-alkyl),C₆-C₂₄ aryloxycarbonyl (—(CO)—O-aryl), halocarbonyl (—CO)—X where X ishalo), C₂-C₂₄ alkylcarbonato (—O—(CO)—O-alkyl), C₆-C₂₄ arylcarbonato(—O—(CO)—O-aryl), carboxy (—COOH), carboxylato (—COO⁻), carbamoyl(—(CO)—NH₂), mono-(C₁-C₂₄ alkyl)-substituted carbamoyl (—(CO)—NH(C₁-C₂₄alkyl)), di-(C₁-C₂₄ alkyl)-substituted carbamoyl (—(CO)—N(C₁-C₂₄alkyl)₂), mono-(C₁-C₂₄ haloalkyl)-substituted carbamoyl (—(CO)—NH(C₁-C₂₄haloalkyl)), di-(C₁-C₂₄ haloalkyl)-substituted carbamoyl (—(CO)—N(C₁-C₂₄haloalkyl)₂), mono-(C₅-C₂₄ aryl)-substituted carbamoyl (—(CO)—NH-aryl),di-(C₅-C₂₄ aryl)-substituted carbamoyl (—(CO)—N(C₅-C₂₄ aryl)₂),di-N—(C₁-C₂₄ alkyl), N—(C₅-C₂₄ aryl)-substituted carbamoyl(—(CO)—N(C₁-C₂₄ alkyl)(C₅-C₂₄ aryl), thiocarbamoyl (—(CS)—NH₂),mono-(C₁-C₂₄ alkyl)-substituted thiocarbamoyl (—(CS)—NH(C₁-C₂₄ alkyl)),di-(C₁-C₂₄ alkyl)-substituted thiocarbamoyl (—(CS)—N(C₁-C₂₄ alkyl)₂),mono-(C₅-C₂₄ aryl)-substituted thiocarbamoyl (—(CS)—NH-aryl), di-(C₅-C₂₄aryl)-substituted thiocarbamoyl (—(CS)—N(C₅-C₂₄ aryl)₂), di-N—(C₁-C₂₄alkyl), N—(C₅-C₂₄ aryl)-substituted thiocarbamoyl (—(CS)—N(C₁-C₂₄alkyl)(C₅-C₂₄ aryl), carbamido (—NH—(CO)—NH₂), cyano (—C≡N), cyanato(—O—C—N), thiocyanato (—S—C≡N), isocyanate (—NisCisO), thioisocyanate(—NisCisS), formyl (—(CO)—H), thioformyl (—(CS)—H), amino (—NH₂),mono-(C₁-C₂₄ alkyl)-substituted amino (—NH(C₁-C₂₄ alkyl), di-(C₁-C₂₄alkyl)-substituted amino (—N(C₁-C₂₄ alkyl)₂), mono-(C₅-C₂₄aryl)-substituted amino (—NH(C₅-C₂₄ aryl), di-(C₅-C₂₄ aryl)-substitutedamino (—N(C₅-C₂₄ aryl)₂), C₂-C₂₄ alkylamido (—NH—(CO)-alkyl), C₆-C₂₄arylamido (—NH—(CO)-aryl), imino (-CRisNH where R includes withoutlimitation hydrogen, C₁-C₂₄ alkyl, C₅-C₂₄ aryl, C₆-C₂₄ alkaryl, C₆-C₂₄aralkyl, etc.), C₂-C₂₀ alkylimino (-CRisN(alkyl), where R includeswithout limitation hydrogen, C₁-C₂₄ alkyl, C₅-C₂₄ aryl, C₆-C₂₄ alkaryl,C₆-C₂₄ aralkyl, etc.), arylimino (-CRisN(aryl), where R includes withoutlimitation hydrogen, C₁-C₂₀ alkyl, C₅-C₂₄ aryl, C₆-C₂₄ alkaryl, C₆-C₂₄aralkyl, etc.), nitro (—NO₂), nitroso (—NO), sulfo (—SO₂—OH), sulfonato(—SO₂—O—), C₁-C₂₄ alkylsulfanyl (—S-alkyl; also termed “alkylthio”),C₅-C₂₄ arylsulfanyl (—S-aryl; also termed “arylthio”), C₁-C₂₄alkylsulfinyl (—(SO)-alkyl), C₅-C₂₄ arylsulfinyl (—(SO)-aryl), C₁-C₂₄alkylsulfonyl (—SO₂-alkyl), C₁-C₂₄ monoalkylaminosulfonyl (—SO₂—N(H)alkyl), C₁-C₂₄ dialkylaminosulfonyl (—SO₂—N(alkyl)₂), C₅-C₂₄arylsulfonyl (—SO₂-aryl), boryl (—BH₂), borono (—B(OH)₂), boronato(—B(OR)₂ where R is alkyl or aryl), phosphono (—P(O)(OH)₂), phosphonato(—P(O)(O⁻)₂), phosphinato (—P(O)(O—)), phospho (—PO₂), and phosphino(—PH₂); and the hydrocarbyl moieties C₁-C₂₄ alkyl (preferably C₁-C₁₂alkyl, more preferably C₁-C₆ alkyl), C₅-C₂₄ aryl (preferably C₅-C₁₄aryl), C₆-C₂₄ alkaryl (preferably C₆-C₁₆ alkaryl), and C₆-C₂₄ aralkyl(preferably C₆-C₁₆ aralkyl), with the proviso that if E³ is hydrogen,then D³ cannot be nil; and where if E⁴ is hydrogen, then D⁴ cannot benil.

In some embodiments, the invention provides a method that produces acompound (i.e., a product, olefin product; e.g., cross metathesisproduct) having a carbon-carbon double bond (e.g., a product internalolefin) in an E:Z ratio greater than about 1:1, greater than about 2:1,greater than about 3:1, greater than about 4:1, greater than about 5:1,greater than about 6:1, greater than about 7:1, greater than about 8:1,greater than about 9:1, greater than about 95:5, greater than about96:4, greater than about 97:3, greater than about 98:2, or in somecases, greater than about 99:1. In some cases, about 100% of thecarbon-carbon double bond produced in the metathesis reaction may havean E configuration. The E or trans selectivity may also be expressed asa percentage of product formed (e.g., cross metathesis product). In somecases, the product (e.g., cross metathesis product) may be greater thanabout 50% E, greater than about 60% E, greater than about 70% E, greaterthan about 80% E, greater than about 90% E, greater than about 95% E,greater than about 96% E, greater than about 97% E, greater than about98% E, greater than about 99% E, or in some cases greater than about99.5% E.

In another example an at least one cross metathesis product comprising aproduct internal olefin, wherein the product internal olefin is in theE-configuration may be represented by the structure of Formula (5):

wherein, D¹⁹ and D²¹ are identical or are independently selected fromnil, CH₂, O, or S; and E¹⁹ and E²¹ are identical or are independentlyselected from hydrogen, hydrocarbyl (e.g., C₁-C₂₀ alkyl, C₅-C₂₀ aryl,C₅-C₃₀ aralkyl, or C₅-C₃₀ alkaryl), substituted hydrocarbyl (e.g.,substituted C₁-C₂₀ alkyl, C₅-C₂₀ aryl, C₅-C₃₀ aralkyl, or C₅-C₃₀alkaryl), heteroatom-containing hydrocarbyl (e.g., C₁-C₂₀ heteroalkyl,C₅-C₂₀ heteroaryl, heteroatom-containing C₅-C₃₀ aralkyl, orheteroatom-containing C₅-C₃₀ alkaryl), and substitutedheteroatom-containing hydrocarbyl (e.g., substituted C₁-C₂₀ heteroalkyl,C₅-C₂₀ heteroaryl, heteroatom-containing C₅-C₃₀ aralkyl, orheteroatom-containing C₅-C₃₀ alkaryl) and, if substituted hydrocarbyl orsubstituted heteroatom-containing hydrocarbyl, wherein the substituentsmay be functional groups (“Fn”) such as halo, hydroxyl, sulfhydryl,C₁-C₂₄ alkoxy, C₅-C₂₄ aryloxy, C₆-C₂₄ aralkyloxy, C₆-C₂₄ alkaryloxy,acyl (including C₂-C₂₄ alkylcarbonyl (—CO-alkyl) and C₆-C₂₄ arylcarbonyl(—CO-aryl)), acyloxy (—O-acyl, including C₂-C₂₄ alkylcarbonyloxy(—O—CO-alkyl) and C₆-C₂₄ arylcarbonyloxy (—O—CO-aryl)), C₂-C₂₄alkoxycarbonyl (—(CO)—O-alkyl), C₆-C₂₄ aryloxycarbonyl (—(CO)—O-aryl),halocarbonyl (—CO)—X where X is halo), C₂-C₂₄ alkylcarbonato(—O—(CO)—O-alkyl), C₆-C₂₄ arylcarbonato (—O—(CO)—O-aryl), carboxy(—COOH), carboxylato (—COO), carbamoyl (—(CO)—NH₂), mono-(C₁-C₂₄alkyl)-substituted carbamoyl (—(CO)—NH(C₁-C₂₄ alkyl)), di-(C₁-C₂₄alkyl)-substituted carbamoyl (—(CO)—N(C₁-C₂₄ alkyl)₂), mono-(C₁-C₂₄haloalkyl)-substituted carbamoyl (—(CO)—NH(C₁-C₂₄ haloalkyl)),di-(C₁-C₂₄ haloalkyl)-substituted carbamoyl (—(CO)—N(C₁-C₂₄haloalkyl)₂), mono-(C₅-C₂₄ aryl)-substituted carbamoyl (—(CO)—NH-aryl),di-(C₅-C₂₄ aryl)-substituted carbamoyl (—(CO)—N(C₅-C₂₄ aryl)₂),di-N—(C₁-C₂₄ alkyl), N—(C₅-C₂₄ aryl)-substituted carbamoyl(—(CO)—N(C₁-C₂₄ alkyl)(C₅-C₂₄ aryl), thiocarbamoyl (—(CS)—NH₂),mono-(C₁-C₂₄ alkyl)-substituted thiocarbamoyl (—(CS)—NH(C₁-C₂₄ alkyl)),di-(C₁-C₂₄ alkyl)-substituted thiocarbamoyl (—(CS)—N(C₁-C₂₄ alkyl)₂),mono-(C₅-C₂₄ aryl)-substituted thiocarbamoyl (—(CS)—NH-aryl), di-(C₅-C₂₄aryl)-substituted thiocarbamoyl (—(CS)—N(C₅-C₂₄ aryl)₂), di-N—(C₁-C₂₄alkyl), N—(C₅-C₂₄ aryl)-substituted thiocarbamoyl (—(CS)—N(C₁-C₂₄alkyl)(C₅-C₂₄ aryl), carbamido (—NH—(CO)—NH₂), cyano (—C≡N), cyanato(—O—C≡N), thiocyanato (—S—C≡N), isocyanate (—N═C═O), thioisocyanate(—N═C═S), formyl (—(CO)—H), thioformyl (—(CS)—H), amino (—NH₂),mono-(C₁-C₂₄ alkyl)-substituted amino (—NH(C₁-C₂₄ alkyl), di-(C₁-C₂₄alkyl)-substituted amino (—N(C₁-C₂₄ alkyl)₂), mono-(C₅-C₂₄aryl)-substituted amino (—NH(C₅-C₂₄ aryl), di-(C₅-C₂₄ aryl)-substitutedamino (—N(C₅-C₂₄ aryl)₂), C₂-C₂₄ alkylamido (—NH—(CO)-alkyl), C₆-C₂₄arylamido (—NH—(CO)-aryl), imino (—CR═NH where R includes withoutlimitation hydrogen, C₁-C₂₄ alkyl, C₅-C₂₄ aryl, C₆-C₂₄ alkaryl, C₆-C₂₄aralkyl, etc.), C₂-C₂₀ alkylimino (—CR═N(alkyl), where R includeswithout limitation hydrogen, C₁-C₂₄ alkyl, C₅-C₂₄ aryl, C₆-C₂₄ alkaryl,C₆-C₂₄ aralkyl, etc.), arylimino (—CR═N(aryl), where R includes withoutlimitation hydrogen, C₁-C₂₀ alkyl, C₅-C₂₄ aryl, C₆-C₂₄ alkaryl, C₆-C₂₄aralkyl, etc.), nitro (—NO₂), nitroso (—NO), sulfo (—SO₂—OH), sulfonato(—SO₂—O), C₁-C₂₄ alkylsulfanyl (—S-alkyl; also termed “alkylthio”),C₅-C₂₄ arylsulfanyl (—S-aryl; also termed “arylthio”), C₁-C₂₄alkylsulfinyl (—(SO)-alkyl), C₅-C₂₄ arylsulfinyl (—(SO)-aryl), C₁-C₂₄alkylsulfonyl (—SO₂-alkyl), C₁-C₂₄ monoalkylaminosulfonyl (—SO₂—N(H)alkyl), C₁-C₂₄ dialkylaminosulfonyl (—SO₂—N(alkyl)₂), C₅-C₂₄arylsulfonyl (—SO₂-aryl), boryl (—BH₂), borono (—B(OH)₂), boronato(—B(OR)₂ where R is alkyl or aryl), phosphono (—P(O)(OH)₂), phosphonato(—P(O)(O)₂), phosphinato (—P(O)(O)), phospho (—PO₂), and phosphino(—PH₂); and the hydrocarbyl moieties C₁-C₂₄ alkyl (preferably C₁-C₁₂alkyl, more preferably C₁-C₆ alkyl), C₅-C₂₄ aryl (preferably C₅-C₁₄aryl), C₆-C₂₄ alkaryl (preferably C₆-C₁₆ alkaryl), and C₆-C₂₄ aralkyl(preferably C₆-C₁₆ aralkyl); with the proviso that if E²¹ is hydrogen,then D²¹ cannot be nil; and where if E¹⁹ is hydrogen, then D¹⁹ cannot benil.

EXPERIMENTAL

In the following examples, efforts have been made to ensure accuracywith respect to numbers used (e.g., amounts, temperature, etc.) but someexperimental error and deviation should be accounted for. Unlessindicated otherwise, temperature is in degrees Celsius and pressure isat or near atmospheric. The examples are to be considered as not beinglimiting of the invention as described herein and are instead providedas representative examples of the catalyst compounds of the invention,of the methods that may be used in their preparation, and of the methodsof using the inventive catalysts.

All manipulations were carried out under an inert atmosphere using anargon-filled glovebox or standard Schlenk techniques. All glassware wasoven dried prior to use. All solvents were anhydrous grade and spargedwith argon before use. All reagents, unless specified, were obtainedfrom commercial sources and used without further purification. Otherreagents, including catalysts C711, C767, C643, C627 and C823 wereprepared according to previously reported literature procedures.Trans-methyl-9-octadecenoate (>97%) and Cis-methyl-9-octadecenoate(>99%) were purchased from TCI.

¹HNMR spectra were obtained at 400 MHz respectively. ¹H were recordedrelative to residual protio-solvent.

GC Methods: Volatile products were analyzed using an Agilent 6850 gaschromatography (GC) instrument with a flame ionization detector (FID).The following conditions and equipment were used:

Method 1: Column: DB-225, 30 m×0.25 mm (ID)×0.25 μm film thickness.

Manufacturer: Agilent

GC and column conditions: Injector temperature: 220° C., Detectortemperature: 220° C.Oven temperature: Starting temperature: 35° C., hold time: 0.5 minutes.

-   -   Ramp rate 10° C./min to 130° C., hold time: 0 minutes.    -   Ramp rate 20° C./min to 220° C., hold time: 5 minutes.

Carrier gas: Helium

Mean gas velocity: 25 cm/secSplit ratio: 20:1Method 2: Column: HP-5, 30 m×0.25 mm (ID)×0.25 μm film thickness.

Manufacturer: Agilent

GC and column conditions: Injector temperature: 250° C., Detectortemperature: 280° C.Oven temperature: Starting temperature: 100° C., hold time: 1 minute

-   -   Ramp rate 10° C./min to 270° C., hold time: 12 minutes.

Carrier gas: Helium

Average velocity: 30 cm/secSplit ratio: 40.8:1

The following abbreviations are used herein:

RT or r.t. room temperature mL milliliter μL microliter CD₂Cl₂deuterated dichloromethane ° C. degrees Celsius h hour g gram mgmilligram THF tetrahydrofuran THF-d₈ deuterated tetrahydrofuran DMSO-d₆deuterated dimethylsulfoxide iPr isopropyl (—CH(CH₃)₂) Zn(OAc)₂ • 2 H₂Ozinc acetate dehydrate HC(OEt)₃ triethyl orthoformate HCl hydrochloricacid PhCl chlorobenzene NaBF₄ sodium tetrafluoroborate NaOtBu sodiumtert-butoxide NaOH sodium hydride LiAlH₄ lithium aluminum hydride KHMDSpotassium bis(trimethylsilyl)amide

3-bromo-2-methylpropene

Example 1

To a 250 mL round bottom flask equipped with a magnetic stir bar wasadded 3,6-dichlorobenzene-1,2-dithiol (2.00 g, 9.47 mmol), Zn(OAc)₂.2H₂O(8.32 g, 37.9 mmol), ethylenediamine (3.80 mL, 56.8 mmol), andisopropanol (100 mL). The resulting suspension was rapidly stirred for24 h at room temperature. The resulting precipitate was isolated byfiltration, washed with methanol (50 mL), hot chloroform (50 mL), thendried under vacuum overnight affording(3,6-dichlorobenzene-1,2-dithiolato)(ethylenediamine)zinc(II) as anlight yellow solid (2.78 g, 87.9%).

¹H NMR (400 MHz, DMSO-d₆) δ 6.78 (br s, 2H), 4.06 (br s, 4H), 2.65 (brs, 4H).

Example 2

In an argon filled glovebox, a 40 mL scintillation vial equipped with amagnetic stir bar was charged with C711 (0.500 g, 0.703 mmol),(3,6-dichlorobenzene-1,2-dithiolato) (ethylenediamine)zinc(II) (259 mg,0.774 mmol), and 15 mL THF. The resulting suspension was stirred for 6 hat room temperature then devolatilized. The resulting residue wasdissolved in a minimal amount of dichloromethane, filtered through a padof celite, recrystallized from dichloromethane/diethyl ether at −30° C.The red/brown crystals were isolated by filtration and dried undervacuum to afford C849z (462 mg, 77.4%).

¹H NMR (400 MHz, CD₂Cl₂) δ 14.52 (s, 1H), 7.52-7.34 (m, 4H), 7.31 (d,J=6.8 Hz, 1H), 7.20 (d, J=6.4 Hz, 1H), 6.86-6.97 (m, 2H), 6.82 (t, Ji=7.3 Hz, 2H), 6.74 (d, J=7.0 Hz, 1H), 6.55 (d, J=6.3 Hz, 1H), 4.97(hept, J=5.6 Hz, 1H), 4.36 (dd, J=20.2, 10.5 Hz, 1H), 4.18 (dd, J=19.1,9.4 Hz, 1H), 4.02 (dd, J=17.6, 9.5 Hz, 1H), 3.96-3.80 (m, 3H), 3.21-2.99(m, 1H), 2.54-2.34 (m, 1H), 1.91 (d, J=5.5 Hz, 3H), 1.43 (d, J=5.8 Hz,3H), 1.38 (d, J=5.9 Hz, 3H), 1.20-1.35 (m, 6H), 1.00-1.10 (m, 6H), 0.94(d, J=5.9 Hz, 3H), 0.54 (d, J=5.6 Hz, 3H), 0.04 (d, J=5.4 Hz, 3H).

Example 3

In an argon filled glovebox, a 40 mL scintillation vial equipped with amagnetic stir bar was charged with C767 (0.150 g, 0.196 mmol),(3,6-dichlorobenzene-1,2-dithiolato)(ethylenediamine)zinc(II) (0.072 g,0.22 mmol), and tetrahydrofuran (10 mL). The resulting suspension wasstirred for 1 hour at ambient temperature then devolatilized. Theresidue was dissolved in dichloromethane (10 mL), filtered through a padof celite, diluted with hexanes (10 mL) then concentrated under vacuum.Reducing the volume to ˜5 mL afforded a yellow/brown microcrystallinesolid which was isolated by filtration, washed with cold hexanes (2×3mL) and dried under vacuum to afford C905 (0.142 g, 80.4%).

¹H NMR (400 MHz, CD₂Cl₂) δ 14.39 (s, 1H), 7.66 (br s, 1H), 7.55 (d,J=1.7 Hz, 2H), 7.44 (t, J=1.8 Hz, 1H), 7.38-7.30 (m, 2H), 6.96 (d, J=8.7Hz, 1H), 6.94 (d, J=8.1 Hz, 1H), 6.86 (d, J=8.1 Hz, 1H), 6.76 (t, J=7.4Hz, 1H), 6.56 (dd, J=7.5, 1.5 Hz, 1H), 6.26 (br s, 1H), 5.05 (septet,J=6.3 Hz, 1H), 4.49-4.38 (m, 1H), 4.08-3.97 (m, 3H), 1.59 (br s, 9H),1.28 (d, J=6.2 Hz, 3H), 1.15 (s, 18H), 1.06 (br s, 9H), 1.02 (d, J=6.4Hz, 3H).

Example 4

C765 was synthesized according to the procedure described in US2014/0371454. C765 was isolated as red/brown crystals in 97.1% yield.

Example 5

To a 500 mL round bottom flask equipped with a magnetic stir bar wasadded 2-methyl-6-fluoroaniline (15.0 mL, 130 mmol),tetrahydrofuran/water (1:1, 200 mL), NaOH (5.19 g, 130 mmol), andtriethylamine (0.90 mL, 6.5 mmol). The suspension was stirred vigorouslyat 0° C. and oxalyl chloride (6.58 mL, 77.8 mmol) was added dropwise.After complete addition, the reaction was stirred for 1 hour whilewarming to ambient temperature. The resulting solid was isolated byfiltration, washed with 1M HCl (50 mL), water (3×50 mL), and diethylether (2×50 mL) then dried under vacuum to affordN¹,N²-bis(2-fluoro-6-methylphenyl)oxalamide (7.05 g, 35.7% yield). ¹HNMR (400 MHz, DMSO-d₆) δ 10.52 (s, 1H), 7.32-7.24 (m, 2H), 7.19-7.11 (m,4H), 2.24 (s, 6H).

Example 6

In an argon filled glovebox, lithium aluminum hydride (3.74 g, 98.6mmol) and tetrahydrofuran/toluene (1:1, 100 mL) were combined in a 500mL round bottom flask equipped with a magnetic stir bar.N¹,N²-bis(2-fluoro-6-methylphenyl)oxalamide (6.00 g, 19.7 mmol) wassubsequently added to the suspension in small portions with stirring.The reaction vessel was sealed, removed from the glovebox, fitted with areflux condenser and heated to 50° C. under argon for 12 h. Aftercooling to ambient temperature the reaction was quenched by slowlyadding water (3.8 mL), followed by aqueous sodium hydroxide (15 wt %,3.8 mL), then an additional portion of water (11.4 mL). The reaction wasstirred rapidly for 2 hours then decanted away from solid residues anddried over magnesium sulfate. Filtration through a pad of celiteafforded a clear solution which was combined with hydrochloric acid (2.0M in ether, 30 mL, 60 mmol). The resulting precipitate was isolated byfiltration then combined with triethyl orthoformate (30 mL) and heatedto 130° C. for 1 hour. After cooling the reaction to ambienttemperature, the precipitate was isolated by filtration, washed withdiethyl ether (2×25 mL), hexanes (2×50 mL), then dried under vacuum toafford 1,3-bis(2-fluoro-6-methylphenyl)-4,5-dihydro-1H-imidazol-3-iumchloride (4.56 g, 71.7% yield).

¹H NMR (400 MHz, DMSO-d₆) δ 9.63 (s, 1H), 7.55-7.47 (m, 2H), 7.38 (t,J=9.2 Hz, 2H), 7.31 (d, J=7.8 Hz, 2H), 4.57 (s, 4H), 2.48 (s, 6H).

Example 7

In an argon filled glovebox, C823 (0.676 g, 0.822 mmol),1,3-bis(2-fluoro-6-methylphenyl)-4,5-dihydro-1H-imidazol-3-ium chloride(0.500 g, 1.64 mmol) and toluene (50 mL) were combined in a 250 mL roundbottom flask equipped with a magnetic stir bar. A solution of potassiumbis(trimethylsilyl)amide (0.328 g, 1.64 mmol) in toluene (20 mL) wassubsequently added and the solution stirred at ambient temperature for 2hours. All volatiles were subsequently removed in vacuum. The resultingresidue was dissolved in dichloromethane (10 mL), filtered through a padof celite, and devolatilized. The crude product was triturated withhexanes (2×20 mL) then recrystallized from toluene/hexanes at ambienttemperature. The crystalline complex was isolated by filtration anddried under vacuum to afford C829 (0.454 g, 66.7% yield).

¹H NMR (400 MHz, CD₂Cl₂) δ 19.28 (s, 1H), 9.4-8.0 (br s 1H), 7.41-7.30(m, 2H). 7.20 (d, J=7.6 Hz, 1H), 7.16-7.04 (m, 3H), 6.90-5.80 (br s,3H), 6.72-6.62 (m, 1H), 4.22-3.75 (m, 4H), 2.75 (pseudo d, J=16.5 Hz,3H), 2.55-2.05 (br s, 3H), 2.11 (pseudo dd, J=22.7, 11.9 Hz, 3H),1.65-1.23 (m, 15H), 1.10-0.72 (m, 15H)

Example 8

In an argon filled glovebox, C829 (0.300 g, 0.362 mmol),1-isopropoxy-2-(prop-1-en-1-yl)benzene (0.638 g, 3.62 mmol) and toluene(10 mL) were combined in a 40 mL scintillation vial equipped with amagnetic stir bar. The reaction was stirred at ambient temperature for14 hours then directly adsorbed onto silica gel. Purification by columnchromatography (silica gel, 2 to 6% gradient of ethyl acetate/hexanes)afforded 0.190 g (90% pure) of crude intermediate. The crudeintermediate was subsequently combined with(3,6-dichlorobenzene-1,2-dithiolato)(ethylenediamine)zinc(II) (0.115 g,0.345 mmol) and tetrahydrofuran (5 mL) in a 20 mL scintillation vialequipped with a magnetic stir bar. After 4 hours of stirring at ambienttemperature, all volatiles were removed, the residue dissolved indichloromethane, filtered through celite, devolatilized andrecrystallized from dichloromethane/diethyl ether at −35° C. Theresulting yellow/brown crystals were isolated by filtration, washed withcold diethyl ether (2×5 mL) then dried under vacuum to afford C745(0.116 g, 35.7% yield).

¹H NMR (400 MHz, CD₂Cl₂) [three conformers in solution, 8:25:67] δ 14.42(s, 0.08H), 14.39 (s, 0.25H), 14.36 (s, 0.67H), 7.37-7.27 (m, 1H),7.26-7.02 (m, 2.7H), 7.02-6.62 (m, 7.3H), 6.41 (s, 0.4H), 6.10 (t, J=9.0Hz, 0.6H), 5.47-5.38 (m, 1H), 4.13-3.86 (m, 4H), 2.61-2.40 (m, 5H),1.85-1.65 (m, 7H).

Example 9

To a 100 mL round bottom flask equipped with a magnetic stir bar wasadded 2,6-difluoroaniline (10.0 mL, 95.9 mmol) and triethyl orthoformate(8.11 mL, 48.8 mmol). To the stirring solution was added hydrochloricacid (0.040 mL, 12 M, 0.48 mmol) and the reaction stirred at ambienttemperature for 10 minutes. The reaction solidified and was subsequentlysonicated for an additional 10 minutes. The resulting precipitate wassubsequently isolated by filtration, washed with hexanes (2×30 mL) thendried under vacuum to afford N,N′-bis(2,6-difluorophenyl)formimidamide(8.47 g, 67.9% yield).

¹H NMR (400 MHz, DMSO-d₆) δ 9.47 (br s, 1H), 8.03 (s, 1H), 7.10 (br s,6H).

Example 10

To a 20 mL scintillation vial equipped with a magnetic stir bar wasadded N,N′-bis(2,6-difluorophenyl)formimidamide (4.00 g, 14.9 mmol),3-bromo-2-methylpropene (1.65 mL, 16.4 mmol), and chlorobenzene (120mL). The reaction was heated to 125° C. for 24 h. After cooling theresulting precipitate was isolated by filtration and washed with diethylether (2×20 mL). The crude product was then partitioned betweendichloromethane and an aqueous sodium tetrafluoroborate solution (100mL, 1:1, 2.0 g NaBF₄/50 mL). The organic layer was separated, dried overmagnesium sulfate, filtered through celite and all volatiles wereremoved by rotary evaporation. The resulting reside was recrystallizedfrom dichloromethane/diethyl ether to afford1,3-bis(2,6-difluorophenyl)-4,4-dimethyl-4,5-dihydro-1H-imidazol-3-iumtetrafluoroborate (3.25 g, 53.1% yield).

¹H NMR (400 MHz, DMSO-d₆) δ 9.59 (s, 1H), 7.79 (m, 1H), 7.70-7.60 (m,1H), 7.55-7.42 (m, 4H), 4.55 (s, 2H), 1.54 (s, 6H).

Example 11

In an argon filled glovebox,1,3-bis(2,6-difluorophenyl)-4,4-dimethyl-4,5-dihydro-1H-imidazol-3-iumtetrafluoroborate (0.500 g, 1.22 mmol), NaOtBu (0.117 g, 1.22 mmol), andC823 (0.502 g, 0.610 mmol) were weighed into separate 40 mLscintillation vials equipped with magnetic stir bars and eachdissolved/suspended in tetrahydrofuran (10 mL). Thesolutions/suspensions were cooled to −35° C. then the solution of NaOtBuwas added to the solution of1,3-bis(2,6-difluorophenyl)-4,4-dimethyl-4,5-dihydro-1H-imidazol-3-iumtetrafluoroborate over 2 minutes. The reaction was stirred at −35° C.for 1 h then combined with the chilled suspension of C823 and stirredfor an additional hour at −35° C. before allowing the reaction to slowlywarm to ambient temperature overnight. The reaction was subsequentlydevolatilized, triturated with hexanes (2×40 mL), dissolved in toluene(10 mL), and filtered through celite. The crude solution was combinedwith a solution of 1-isopropoxy-2-(prop-1-en-1-yl)benzene (0.400 g, 2.27mmol) in toluene (2 mL) and stirred overnight at ambient temperature.The resulting green precipitate was isolated by filtration, washed withtoluene/hexanes (1:3, 2×10 mL) then dried under vacuum to afford C642(0.221 g, 56.4% yield).

¹H NMR (400 MHz, CD₂Cl₂) δ 16.76 (s, 1H), 7.59-7.54 (m, 1H), 7.53-7.41(m, 2H), 7.17-7.07 (m, 5H), 6.98-6.90 (m, 2H), 5.07-4.96 (sept, J=6.2Hz, 1H), 4.06 (s, 2H), 1.49 (s, 3H), 1.48 (s, 3H), 1.42 (d, J=6.1 Hz,6H).

Example 12

In an argon filled glovebox, C642 (0.150 g, 0.234 mmol) and(3,6-dichlorobenzene-1,2-dithiolato)(ethylenediamine)zinc(II) (0.086 g,0.26 mmol) were combined in a 20 mL scintillation vial equipped with amagnetic stir bar and dissolved in tetrahydrofuran (10 mL). The reactionwas stirred for 60 minutes then devolatilized, dissolved indichloromethane, filtered, and recrystallized fromdichloromethane/diethyl ether at −35° C. The resulting yellow/browncrystals were washed with cold diethyl ether (2×3 mL) then dried undervacuum to afford C781 (0.128 g, 70.2% yield). ¹H NMR (400 MHz, CD₂Cl₂)[two conformers in solution, 40:60] δ 14.52 br s (0.4H), 14.43 (br s,0.6H), 7.33 (t, J=7.4 Hz, 1H), 7.08 (d, J=8.4 Hz, 1H), 7.05-6.67 (m,9H), 6.13 (br s, 1H), 5.42 (br s, 1H), 3.94 (br q, J=8.0 Hz, 1.2H), 3.78(br s, 0.8H), 1.88-1.74 (m, 6H), 1.50-1.28 (m, 6H).

Example 13

To a 100 mL round bottom flask equipped with a magnetic stir bar wasadded 2,4,6-difluoroaniline (10.0 g, 68.0 mmol), hexanes (25 mL), andtriethyl orthoformate (5.94 mL, 35.7 mmol). To the stirring solution wasadded hydrochloric acid (0.180 mL, 2 M in diethyl ether, 0.36 mmol) andthe reaction stirred at ambient temperature for 60 minutes. Theresulting precipitate was subsequently isolated by filtration, washedwith hexanes (2×10 mL) then dried under vacuum to affordN,N-bis(2,4,6-difluorophenyl)formimidamide (7.73 g, 74.8% yield).

¹H NMR (400 MHz, DMSO-d₆) δ 9.27 (br s, 1H), 7.98 (s, 1H), 7.19 (br s,4H).

Example 14

To a 40 mL scintillation vial equipped with a magnetic stir bar wasadded N,N′-bis(2,4,6-trifluorophenyl)formimidamide (0.511 g, 1.68 mmol),3-bromo-2-methylpropene (0.200 mL, 1.97 mmol), and ortho-dichlorobenzene(4 mL). The reaction was heated to 120° C. for 60 h. After cooling to 0°C. the resulting precipitate was isolated by filtration and washed withhexanes (3×15 mL). The crude product was then partitioned betweendichloromethane and an aqueous sodium tetrafluoroborate solution (30 mL,1:1, 0.75 g NaBF₄/15 mL). The organic layer was separated and allvolatiles were removed by rotary evaporation affording1,3-bis(2,6-difluorophenyl)-4,4-dimethyl-4,5-dihydro-1H-imidazol-3-iumtetrafluoroborate (0.339 g, 45.2% yield).

¹H NMR (400 MHz, DMSO-d₆) δ 9.49 (s, 1H), 7.71-7.59 (m, 4H), 4.48 (s,2H), 1.52 (s, 6H).

Example 15

In an argon filled glovebox,1,3-bis(2,4,6-difluorophenyl)-4,4-dimethyl-4,5-dihydro-1H-imidazol-3-iumbromide (0.300 g, 0.683 mmol), sodium tert-butoxide (0.0656 g, 0.683mmol), and C823 (0.281 g, 0.342 mmol) were weighed into separate 40 mLscintillation vials equipped with magnetic stir bars and eachdissolved/suspended in tetrahydrofuran (10 mL). Thesolutions/suspensions were cooled to −35° C. then the solution of sodiumtert-butoxide was added to the solution of1,3-bis(2,4,6-difluorophenyl)-4,4-dimethyl-4,5-dihydro-1H-imidazol-3-iumbromide over 2 minutes. The reaction was stirred at −35° C. for 30minutes then combined with the chilled suspension of C823 and stirredfor an additional 30 minutes at −35° C. before allowing the reaction toslowly warm to ambient temperature overnight. The reaction wassubsequently devolatilized, triturated with hexanes (2×40 mL), dissolvedin toluene (10 mL), and filtered through celite. The crude solution wascombined with a solution of 1-isopropoxy-2-(prop-1-en-1-yl)benzene(0.301 g, 1.71 mmol) in toluene (2 mL) and stirred overnight at ambienttemperature. The resulting solution was diluted with hexanes (15 mL) toafford a green precipitate which was isolated by filtration and washedwith toluene/hexanes (1:10, 2×10 mL). The precipitate was dissolved intetrahydrofuran (5 mL) and combined with(3,6-dichlorobenzene-1,2-dithiolato)(ethylenediamine)zinc(II) (0.086 g,0.26 mmol) in a 20 mL scintillation vial equipped with a magnetic stirbar. The resulting reaction was stirred at ambient temperature for 60minutes then devolatilized, dissolved in dichloromethane, filtered, andrecrystallized from dichloromethane/diethyl ether at −35° C. Theresulting yellow/brown crystals were washed with cold diethyl ether (2×3mL) then dried under vacuum to afford C817 (0.0462 g, 16.5% yieldoverall).

¹H NMR (400 MHz, CD₂Cl₂) [two conformers in solution, 40:60] δ 14.54 brs (0.4H), 14.44 (br s, 0.6H), 7.43-7.34 (m, 1H), 7.11 (d, J=8.6 Hz, 1H),6.97-6.89 (m, 2H), 6.88-6.81 (m, 2H), 6.77-6.67 (m, 1H), 6.40-6.64 (m,2H), 5.95-5.82 (m, 1H), 5.52-5.35 (m, 1H), 3.90 (br s, 1.2H), 3.75 (brs, 0.8H), 1.88-1.74 (m, 6H), 1.45-1.29 (m, 6H).

Stereoretentive Self-Metathesis of Internal Olefins Example 16Self-Metathesis of cis or trans-5-Tetradecene (5C14)

In an argon filled glovebox, a 20 mL scintillation vial equipped with amagnetic stir bar was charged with C765 (4.5 mg, 0.0059 mmol) andtetrahydrofuran (1 mL). 5-Tetradecene (cis or trans) (0.150 mL, 0.588mmol) was subsequently added, the vial sealed and heated to 40° C. for 2hours. Yields and stereoselectivies were determined by gaschromatography (method 1).

TABLE 1

5C14 (cis:trans) % 5C14 (Z/E) % 5C10 (Z/E) % 9C18 cis > 98% 50 (97/3) 25(97/3) 25 trans > 98% 54 (4/96) 23 (5/95) 23

Unexpectedly, after 2 hours at 40° C., reactions of either cis ortrans-5C14 (>98% stereoisomerically pure) catalyzed by 1 mol % C765reached a near equilibrium distribution of products while retaining thestereochemistry of the starting material in high fidelity.

Example 17 Self-Metathesis of Various Ratios of cis andtrans-5-Tetradecene (5C14)

In an argon filled glovebox, a 20 mL scintillation vial equipped with amagnetic stir bar was charged with C765 (4.5 mg, 0.0059 mmol) andtetrahydrofuran (1 mL). 5-Tetradecene (cis/trans) (0.150 mL total, 0.588mmol) in an appropriate ratio was subsequently added, the vial sealedand stirred at ambient temperature. Reactions were sampled at 2 and 4hour time points and yields/stereoselectivies were determined by gaschromatography (method 1).

TABLE 2

time entry 5C14 (cis:trans) (h) % 5C14 (Z/E) % 5C10 (Z/E) % 9C18 1 cis >98% 2 54 (95/5) 23 (95/5) 23 4 52 (94/6) 24 (94/6) 24 2 90:10 2 54(74/26) 23 (90/10) 23 4 53 (72/28) 23 (87/13) 24 3 50:50 2 64 (36/64) 18(73/27) 18 4 63 (36/64) 19 (68/32) 18 4 10:90 2 86 (9/91) 7 (49/51)  7 484 (8/92) 8 (47/53)  8 5 trans > 98% 2 82 (2/98) 9 (11/89)  9 4 80(2/98) 10 (10/90) 10

Table 2 summarizes a series of reactions where C765 (0.5 mol %) wasexposed to various ratios of cis and trans-5C14. While goodstereoretention is attainable when isomerically pure starting materialis used (entries 1 and 5), product distributions from reactions withmixtures of cis and trans-5C14 were complicated by the difference inreactivity of cis and trans stereoisomers.

Example 18 Self-Metathesis of cis-5-Tetradecene (5C14)

In an argon filled glovebox, a 20 mL scintillation vial equipped with amagnetic stir bar was charged with C849z (10-5000 ppm) andtetrahydrofuran (1 mL). cis-5-Tetradecene (0.150 mL, 0.588 mmol) wassubsequently added, the vials sealed and stirred at ambient temperature.Reactions were sampled at appropriate time intervals andyields/stereoselectivies were determined by gas chromatography (method1).

TABLE 3

C849z time % % entry (ppm) (min) % 5C14 (Z/E) % 5C10 (Z/E) 9C18 isomers1 5000  30 47 (92/8) 23 (91/9) 24 6  60 42 (90/10) 21 (88/12) 22 15 12036 (81/19) 18 (81/19) 18 28 2 1000  30 50 (95/5) 25 (95/5) 24 1  60 49(94/6) 25 (94/6) 24 2 3  500  30 49 (95/5) 25 (96/4) 25 1  60 50 (95/5)25 (95/5) 24 1 4  100  30 52 (96/4) 24 (96/4) 24 <1  60 52 (96/4) 24(96/4) 24 <1 5  50  30 51 (95/5) 25 (96/4) 24 <1  60 51 (94/6) 25 (96/4)24 <1

We increased the steric bulk of the NHC ligand and prepared C849z.Reactions of C849z with cis-5C14 were initially hindered by highcatalyst activity (entry 1), as a loading of 5000 ppm (0.5 mol %)afforded a significant amount of isomers and eroded thestereoselectivity of the transformation rapidly. Reducing the catalyticcharge (1000 to 50 ppm; entries 2-5) afforded equilibrium distributionswithin 1 hour with good stereoretention.

Example 19 Self-Metathesis of Various Ratios of cis andtrans-5-Tetradecene (5C14)

In an argon filled glovebox, a 20 mL scintillation vial equipped with amagnetic stir bar was charged with C849z (500 ppm) and tetrahydrofuran(1 mL). 5-Tetradecene (cis/trans) (0.150 mL total, 0.588 mmol) in anappropriate ratio was subsequently added, the vial sealed and stirred atambient temperature. Reactions were sampled at appropriate timeintervals and yields/stereoselectivies were determined by gaschromatography (method 1).

TABLE 4

5C14 time entry (cis:trans) (min) % 5C14 (Z/E) % 5C10 (Z/E) % 9C18 1cis > 98%  30 63 (95/5) 19 (95/5) 18  60 56 (94/6) 22 (95/5) 22 120 54(93/7) 23 (95/5) 23 240 54 (93/7) 24 (95/5) 23 2 90:10  30 60 (77/23) 20(96/4) 20  60 57 (76/24) 21 (96/4) 21 120 57 (75/25) 22 (96/4) 21 240 57(75/25) 22 (96/4) 21 3 50:50  30 74 (33/67) 13 (92/8) 13  60 73 (33/67)14 (90/10) 13 120 73 (33/67) 14 (88/12) 14 240 73 (33/67) 14 (88/12) 144 10:90  30 91 (7/93) 4 (80/20) 4  60 91 (8/92) 5 (74/26) 5 120 91(8/92) 5 (72/28) 5 240 91 (8/92) 5 (72/28) 5 5 trans > 98%  30 98 (2/98)1 (64/36) <1  60 97 (2/98) 1 (61/39) 1 120 97 (2/98) 1 (59/41) 1 240 97(2/98) 1 (58/42) 1

Using an optimized catalyst loading, Table 4 summarizes a series ofreactions where C849z (500 ppm) was exposed to various ratios of cis andtrans-5C14. Unlike C765, C849z afforded product distributions thatapproach theoretical, when the trans-5-tetradecene is considered anunreactive stereoisomer.

Example 20 Self-Metathesis of cis or trans-Methyl-9-octadecenoate (MO)

In an argon filled glovebox, a 20 mL scintillation vial equipped with amagnetic stir bar was charged with either C765 (0.5-7.5 mol %) or C849z(100 ppm) and tetrahydrofuran (1 mL). Methyl-9-octadecenoate (cis ortrans) (0.150 mL, 0.442 mmol) was subsequently added, the vial sealedand stirred at ambient temperature. Reactions were sampled atappropriate time intervals and yields/stereoselectivies were determinedby gas chromatography (method 2). DE is 1,18-dimethyl ester of9-octadecene and 9C18 is 9-octadecene.

TABLE 5

entry Ru (mol %) MO (cis:trans) time (h) % MO (Z/E) % DE (Z/E) % 9C18(Z/E) 1 C849z (0.01) cis > 99% 0.5 64 (>99/1) 18 (>99/1) 18 (>99/1) 1.553 (>99/1) 23 (>99/1) 24 (>99/1) 2 52 (>99/1) 24 (>99/1) 24 (>99/1) 2C849z (0.01) trans > 97% 0.5 100 (<1/99) ND^(a) ND^(a) 1.5 100 (<1/99)ND^(a) ND^(a) 2 100 (<1/99) ND^(a) ND^(a) 3 C765 (0.5) cis > 99% 0.5 90(>99/1) 5 (>99/1) 5 (>99/1) 1.5 84 (>99/1) 8 (>99/1) 8 (>99/1) 2 80(>99/1) 10 (>99/1) 10 (>99/1) 4 C765 (0.5) trans > 97% 2 100 (<1/99)ND^(a) ND^(a) 5 C765 (2.5) trans > 97% 4 98 (<1/99) 1 (<1/99) 1 (<1/99)20 92 (<1/99) 4 (<1/99) 4 (<1/99) 6 C765 (5.0) trans > 97% 4 93 (<1/99)3 (<1/99) 3 (<1/99) 20 72 (1/99) 14 (3/97) 14 (3/97) 7 C765 (7.5)trans > 97% 4 80 (<1/99) 10 (<1/99) 10 (<1/99) 20 52 (4/96) 24 (4/96) 24(4/96) ^(a)not detected

The self-metathesis of methyl-9-octadecenoate (MO) was subsequentlyexamined to determine the effect of modest functionality on thetransformation (Table 5). Exposing cis-methyl-9-octadecenoate to C849z(0.1 mol %) afforded an equilibrium distribution of product within 2hours with excellent stereoretention (>99% Z) (entry 1). At this sameloading, no reaction was observed with trans-methyl-9-octadecenoate(entry 2). A higher catalyst loading of C765 (0.5 mol %) afforded 20%conversion of cis-methyl-9-octadecenoate while failing to afford anyreaction with trans-methyl-9-octadecenoate after 2 hours (entries 3 and4). Increasing the catalyst loading of C765 restored reactivity withtrans-methyl-9-octadecenoate (entries 5-7) and after 20 hours, C765 (7.5mol %) afforded a near equilibrium distribution of products with goodstereoretention (96% E).

Example 21 Self-Metathesis of Various Ratios of cis andtrans-Methyl-9-octadecenoate (MO)

In an argon filled glovebox, a 20 mL scintillation vial equipped with amagnetic stir bar was charged with C849z (1000 ppm) and tetrahydrofuran(1 mL). Methyl-9-octadecenoate (cis/trans) (0.150 mL total, 0.442 mmol)was subsequently added, the vial sealed and stirred at ambienttemperature. Reactions were sampled at appropriate time intervals andyields/stereoselectivies were determined by gas chromatography (method2).

TABLE 6

entry MO (cis:trans) time (min) % MO (Z/E) % DE % 9C18 (Z/E) 1 cis > 99% 30 50 (>99/1) 25 25 (>99/1)  60 50 (>99/1) 25 25 (>99/1) 120 50 (>99/1)25 25 (>99/1) 240 50 (>99/1) 25 25 (98/2) 2 80:20  30 80 (75/25) 10 10(>99/1)  60 72 (72/27) 14 14 (97/3) 120 68 (70/30) 16 16 (97/3) 240 66(68/32) 17 17 (96/4) 3 50:50  30 91 (46/54)  5 5 (>99/1)  60 88 (44/56) 6 6 (>99/1) 120 86 (42/58)  7 7 (>99/1) 240 85 (42/58)  7 7 (>99/1) 420:80  30 100 (20/80) ND^(a) ND^(a)  60 99 (20/80) <1 <1 (>99/1) 120 99(20/80)  1 1 (>99/1) 240 99 (20/80)  1 1 (>99/1) 5 trans > 97%  30 100(<1/99) ND^(a) ND^(a)  60 100 (<1/99) ND^(a) ND^(a) 120 100 (<1/99)ND^(a) ND^(a) 240 100 (<1/99) ND^(a) ND^(a) ^(a)not detected

Table 6 summarizes a series of reactions where C849z (1000 ppm) wasexposed to various ratios of cis and trans-methyl-9-octadecenoate.Reactions with 80 or 100% cis-methyl-9-octadecenoate (entries 1 and 2)afforded near theoretical product distributions after 4 hours withexcellent stereoretention. Reactions conducted with an increasedtrans-methyl-9-octadecenoate content (entries 3-5) afforded very littlereactivity although products maintained high fidelity.

Example 22 Self-Metathesis of cis or trans-2-Hexene

In an argon filled glovebox, a 40 mL scintillation vial equipped with amagnetic stir bar was charged with catalyst and tetrahydrofuran (1 mL).2-Hexene (cis or trans) (0.100 mL, 0.815 mmol) was subsequently added,the vial sealed and stirred at ambient temperature. Reactions weresampled at appropriate time intervals and yields/stereoselectivies weredetermined by gas chromatography (method 1).

TABLE 7

entry Ru (mol %) cis/trans time (h) % conv % yield Z/E 1 C849z (0.05)cis 1 48 44 98/2  2 49 44 97/3  6 50 44 96/4  2 trans 1 NR^(a) NR^(a)ND^(b) 2 NR^(a) NR^(a) ND^(b) 6 NR^(a) NR^(a) ND^(b) 3 C765 (0.5) cis 148 44 98/2  2 49 44 97/3  6 51 44 92/8  4 trans 1 <1 <1 ND^(b) 2 2 236/64 6 4 4 25/75 5 C745 (0.5) cis 1 46 44 99/1  2 48 44 97/3  6 50 4594/6  6 trans 1 1 1 <1/99 2 4 4 <1/99 6 23 23 <1/99 ^(a)no reactionobserved ^(b)not determined

While C849z, in comparison with C765, afforded a greater disparity inthe reactivity of cis and trans substrates, we sought to identify acatalyst with an improved rate of reactivity with trans substrates.Reducing the steric bulk of the ortho-substituents of the NHC ligandafforded C745. C849z, C765 and C745 were subsequently screened ascatalysts for the self-metathesis of 2-hexene (Table 7). Reactions ofcis-2-hexene (entries 1, 3, and 5) reached maximum conversion/yieldwithin 1 hour with excellent stereoretention (>98% Z). Under the sameconditions, trans-2-hexene afforded little to no conversion (<4%) after6 hours when exposed to C765 (0.5 mol %) or C849z (0.05 mol %) (entries2 and 4). Gratifyingly, C745 (0.5 mol %) afforded 23% yield after 6hours with excellent stereoretention (>99% E) (entry 6).

Stereoretentive Cross Metathesis of Internal Olefins Example 23 CrossMetathesis of 4-Octene (4C8) with 1,4-Diacetoxy-2-butene (1,4-DAB)

In an argon filled glovebox, a 20 mL scintillation vial equipped with amagnetic stir bar was charged with catalyst and tetrahydrofuran (0.50mL). 4-Octene (0.100 mL, 0.64 mmol) and 1,4-diacetoxy-2-butene (0.406mL, 2.55 mmol) were subsequently added, the vial sealed and stirred atambient temperature. Reactions were sampled at appropriate timeintervals and yields/stereoselectivies were determined by gaschromatography (method 2).

TABLE 8

C765 entry (mol %) 4C8/1,4-DAB time (h) % conv % yield^(a) Z/E^(a) 1 3.0cis/cis 0.25 54 49 >99/1 1.5 94 91 >99/1 2.5 95 91 >99/1 5 95 91 >99/1 25.0 trans/trans 1  9  6 <1/99 2 15 11 <1/99 4 19 17 <1/99 5 22 20 <1/9972 33 31 <1/99 3 7.5 trans/trans 1 15 11 <1/99 2 21 19 <1/99 4 30 27<1/99 5 33 31 <1/99 72 50 47 <1/99 ^(a)2-hexenyl acetate (2C6 OAc)

The cross metathesis of 4-octene and 1,4-diacetoxy-2-butene was examined(Table 8). Contacting a mixture of cis-1,4-diacetoxy-2-butene andcis-4-octene (4:1) with C765 (3.0 mol %) afforded cis-2-hexenyl acetatein 91% yield (>99% Z) (entry 1). Reactions betweentrans-1,4-diacetoxy-2-butene and trans-4-octene were considerably slower(entries 2 and 3) but after 3 days, a mixture oftrans-1,4-diacetoxy-2-butene and trans-4-octene (4:1) with C765 (7.5 mol%) afforded trans-2-hexenyl acetate in 47% yield (>99% E).

Example 24 Cross Metathesis of trans-4-Octene withtrans-1,4-Diacetoxy-2-butene

In an argon filled glovebox, a 4 mL scintillation vial equipped with amagnetic stir bar was charged with catalyst and tetrahydrofuran (1 mL).Trans-4-octene (0.050 mL, 0.32 mmol) and trans-1,4-diacetoxy-2-butene(0.203 mL, 1.27 mmol) were subsequently added, the vial was sealed andstirred at ambient temperature. Reactions were sampled at appropriatetime intervals and yields/stereoselectivies were determined by gaschromatography (method 2).

TABLE 9

entry Ru time (h) % yield^(a) Z/E^(a) 1 C765  1  0 ND^(b)  2  2 <1/99  4 4 <1/99 72 13 <1/99 2 C745  1  2 <1/99  2  5 <1/99  4 11 <1/99 72 24<1/99 3 C781  1  4 <1/99  2  7 <1/99  4 14 <1/99 72 28 <1/99 4 C817  1 3 <1/99  2  6 <1/99  4 11 <1/99 72 27 <1/99 5 C905  1  2 <1/99  2  2<1/99  4  4 <1/99 48  4 <1/99 ^(a)2C6 OAc ^(b)not determined

Focusing our efforts on identifying catalysts with improved reactivitytoward trans substrates, C781, C817 and C905 were prepared. Contacting amixture of trans-1,4-diacetoxy-2-butene and trans-4-octene (4:1) withruthenium catalyst (3.0 mol %) afforded trans-2-hexenyl acetate (Table9). After 3 days, C765 afforded 13% yield of trans-2-hexenyl acetate(entry 1) whereas C745, C781 and C817 afforded 24-28% yield (entries2-4). C905 performed poorly affording <5% yield (entry 5).

Stereoretentive Cross Metathesis of Terminal Olefins with InternalOlefins Example 25 Cross Metathesis of Allyl acetate with cis ortrans-4-Octene

In an argon filled glovebox, a 20 mL scintillation vial equipped with amagnetic stir bar was charged with catalyst and tetrahydrofuran (1 mL).4-Octene (cis or trans) (0.120 mL, 0.75 mmol) and allyl acetate (0.050mL, 0.38 mmol) were subsequently added, the vial sealed and stirred at30° C. Reactions were sampled at appropriate time intervals andyields/stereoselectivies were determined by gas chromatography (method2).

TABLE 10

entry cis/trans Ru time (h) % conv % yield^(a) Z/E^(a) 1 cis C765  2 2828 >99/1  4 28 28 >99/1 22 28 28 >99/1 2 trans C765  2 ND^(b) ND^(b)ND^(b)  4 ND^(b) ND^(b) ND^(b) 22 ND^(b) ND^(b) ND^(b) 3 cis C849z  2 2222 >99/1  4 22 22 >99/1 22 22 22 >99/1 4 trans C849z  2 ND^(b) ND^(b)ND^(b)  4 ND^(b) ND^(b) ND^(b) 22 ND^(b) ND^(b) ND^(b) ^(a)2C6 OAc^(b)not detected

A mixture of allyl acetate and cis or trans-4-octene was combined withC849z or C765 (3 mol %) (Table 10). After 22 hours, reactions ofcis-4-octene and C849z or C765 afforded 22 and 28% yield ofcis-2-hexenyl acetate (>99% Z), respectively (entries 1 and 3). Noreactions were observed with trans-4-octene under these conditions(entries 2 and 4).

Example 26 Cross Metathesis of Allyl benzene with cis or trans-4-Octene

In an argon filled glovebox, a 20 mL scintillation vial equipped with amagnetic stir bar was charged with catalyst and tetrahydrofuran (1 mL).4-Octene (cis or trans) (0.120 mL, 0.75 mmol) and allyl benzene (0.059mL, 0.38 mmol) were subsequently added, the vial sealed and stirred atambient temperature. Reactions were sampled at appropriate timeintervals and yields/stereoselectivies were determined by gaschromatography (method 2).

TABLE 11

entry Ru cis/trans time (h) % conv % yield^(a) Z/E^(a) 1 C849z cis 2 9177 99/1  4 92 77 99/1  2 trans 2 31  2 <1/99 4 33  2 <1/99 3 C765 cis 255 45 93/7  4 61 46 88/12 4 trans 2 23  9  8/92 4 31  9 10/90 5 C745 cis2 81 61 96/4  4 82 62 95/5  6 trans 2 60 32 3/97  4 64 32 3/97 ^(a)1-phenyl-2-hexene 1Ph2C6

A mixture of allyl benzene and cis or trans-4-octene was combined withC849z, C765 or C745 (3 mol %) (Table 11). After 4 hours, reactions withcis-4-octene and C849z, C765 or C745 afforded 77, 46, and 62% yieldrespectively (entries 1, 3, and 5) with good stereoretention.Conversions were 10-20% higher than the observed yields with the majorbyproduct resulting from secondary self-metathesis of 1-phenyl-2-hexeneto afford 1,4-diphenyl-2-butene. Reactions were conducted in the samefashion with trans-4-octene and C849z, C765 or C745 afforded 2, 9, and32% yield respectively (entries 2, 4, and 6) with good to excellentstereoretention. Conversions were 20-30% higher than the observed yieldswith the major byproduct resulting from isomerization of allyl benzeneto (3-methylstyrene.

Example 27 Cross Metathesis of 1-Decene (1C10) with cis ortrans-4-Octene

In an argon filled glovebox, a 20 mL scintillation vial equipped with amagnetic stir bar was charged with catalyst and tetrahydrofuran (1 mL).4-Octene (cis or trans) (0.083 mL, 0.53 mmol) and 1-decene (0.050 mL,0.26 mmol) were subsequently added, the vial sealed and stirred atambient temperature. Reactions were sampled at appropriate timeintervals and yields/stereoselectivies were determined by gaschromatography (method 1).

TABLE 12

entry Ru cis/trans time (h) % conv % yield^(a) Z/E^(a) 1 C849z cis 2 9075 97/3  5 89 74 96/4  2 trans 2 91  4 12/88 5 92  4 13/88 3 C765 cis 279 64 96/4  5 87 64 90/10 4 trans 2 28 11  9/91 5 48 13 13/87 5 C745 cis2 86 71 93/7  5 88 73 92/8  6 trans 2 63 46  6/94 5 67 47  7/93 ^(a)4C13

A mixture of 1-decene and cis or trans-4-octene was combined with C849z,C765 or C745 (3.0 mol %) in tetrahydrofuran (1.0 mL) (Table 12). After 5hours, reactions with cis-4-octene and C849z, C765 or C745 afforded 74,64, and 73% yield of cis-4-tridecene (4C13), respectively, with goodstereoretention (entries 1, 3, and 5). Conversions were 15-23% higherthan the observed yields with the major byproduct (9-octadecene)resulting from secondary self-metathesis. Exchanging cis-4-octene withtrans-4-octene afforded less productive reactions as C849z, C765 or C745afforded 4, 13, and 47% yield of trans-4-tridecene, respectively, withgood stereoretention (entries 2, 4, and 6). Conversions for alltransformations were significantly higher than the yields observed(20-88%) and can be attributed to undesired isomerization of 1-decene to2-decene and 4-octene to 3-octene. The isomerized products also formcis-trans isomers which are proposed to attribute to the 4% product inentry 2. 9-Octadecene is observed which results for the product4-tetradecene undergoing additional metathesis to yield 9-octadecene and4-octene.

Example 28 Cross Metathesis of 1-Decene with cis or trans-4-Octene

In an argon filled glovebox, a 4 mL scintillation vial equipped with amagnetic stir bar was charged with catalyst and tetrahydrofuran (2 mL).4-Octene (cis or trans) (0.125 mL, 0.79 mmol) and 1-decene (0.050 mL,0.26 mmol) were subsequently added, the vial sealed and stirred atambient temperature. Reactions were sampled at appropriate timeintervals and yields/stereoselectivies were determined by gaschromatography (method 1).

TABLE 13

entry Ru cis/trans time (h) % conv % yield^(a) Z/E^(a) 1 C765 cis 1 8455 >99/1  2 85 55 >99/1  4 84 58 >99/1  2 trans 1 36  7 <1/99 2 36  7<1/99 4 36  7 <1/99 3 C745 cis 1 82 58 >99/1  2 87 59 97/3  4 88 5797/3  4 trans 1 50 21 <1/99 2 54 26 <1/99 4 53 29 <1/99 5 C781 cis 1 6642 >99/1  2 74 49 >99/1  4 79 54 >99/1  6 trans 1 43 19 <1/99 2 51 25<1/99 4 53 31 <1/99 7 C817 cis 1 56 48 98/2  2 58 57 98/2  4 76 65 97/3 8 trans 1 32 25  1/99 2 42 32  2/98 4 50 39  2/98 9 C905 cis 1 21 2187/13 2 25 24 87/13 4 25 24 87/13 10 trans 1 ND^(b) ND^(b) ND^(b) 2ND^(b) ND^(b) ND^(b) 4 ND^(b) ND^(b) ND^(b) ^(a)4-tridecene 4C13 ^(b)notdetected

A mixture of 1-decene and cis-4-octene was combined with C765, C745,C781, C817, or C905 (3.0 mol %) in tetrahydrofuran (2.0 mL) (Table 13).After 4 hours, C765, C745, C781 and C817 afforded 54-65% yield ofcis-4-tridecene with excellent stereoretention (>97% Z) (entries 1, 3,5, and 7). Exchanging cis-4-octene with trans-4-octene afforded lessproductive reactions as C765, C745, C781 and C817 afforded 7-39% yieldof trans-4-tridecene with excellent stereoretention (>98% E) (entries 2,3, 6, and 8). C905 performed poorly affording only 24% for the crossmetathesis of 1-decene and cis-4-octene and no reaction was observedwith trans-4-octene.

Example 29

Self-metathesis reaction

Substrate Time (hr) % E 5 % E 6 % E 4 4a^(a) 0.5 >97 >97 >98 1 >98 >9699 2 >97 >98 98 5 >99 >98 >99 4b^(a) 0.5 100.0 100.0 100.0 1 >98 100.0100.0 2 >99 >99 98 5 99 >97 98 ^(a)Quantitative data determined by gaschromatography.

Example 30

Self-metathesis reaction

Percent Substrate Time (hr) % E 5 % E 6 % E 4 Conversion 4c^(a) 1 >98 >98 >98 3.9  7 >98 >98 >98 9.5 12 >98 >98 >98 12.4 18 >98 >98 >9813.3 23 >98 >98 >98 14.2 4d^(a)  1 >98 >98 >98 2.1  7 >98 >98 >98 6.812 >98 >98 >98 9.6 18 >98 >98 >98 12.0 22 >98 >98 >98 13.2^(a)Quantitative data determined by ¹H NMR. Reactions were ran in a J.Young tube in THF-d₈.

Example 31

Cross metathesis reaction

Percent Time (hr) % E 7^(a) % E 8^(a) % E 9^(a) Conversion^(a) 1 >98 >98 >98  0.8  7 >98 >98 >98  4.2 12 >98 >98 >98  6.418 >98 >98 >98  8.2 24 >98 >98 >98  9.9 48 >98 >98 >98 12.5^(a)Quantitative data determined by ¹H NMR. Reactions were ran in a J.Young tube in THF-d₈.

1.-8. (canceled)
 9. A compound selected from:


10. A method for performing a cross metathesis reaction, comprising:contacting a first olefin reactant with a second olefin reactant in thepresence of a compound according to claim 9, under conditions effectiveto promote the formation of at least one cross metathesis product. 11.The method according to claim 10, wherein the first olefin reactant andthe second olefin reactant are the same.
 12. The method according toclaim 10 wherein the first olefin reactant and the second olefinreactant are different.
 13. The method according to claim 10, whereinthe first olefin reactant and the second olefin reactant are each in aZ-configuration.
 14. The method according to claim 13, wherein the atleast one cross metathesis product is greater than about 80% Z.
 15. Themethod according to claim 10, wherein the first olefin reactant and thesecond olefin reactant are each in an E-configuration.
 16. The methodaccording to claim 15, wherein the at least one cross metathesis productis greater than about 80% E.